Detergent and liquid soap compositions comprising biologically-based mono and di esters

ABSTRACT

A process for providing detergent compositions comprising synthesizing mono and di esters from biologically derived 1,3-propanediol an incorporating said esters into detergent formulations. The basic process involves producing and purifying biologically derived 1,3-propanediol, synthesizing mono and di esters by the condensation of 1,3-propanediol with an acid using a catalyst, recovering the ester and incorporating said ester into a detergent formulation. The compositions made from the biologically derived 1,3-propanediol are also encompassed by the invention.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of U.S. Provisional Application Ser. No. 60/772,471, filed Feb. 10, 2006; U.S. Provisional Application No. 60/772,194, filed Feb. 10, 2006, U.S. Provisional Application No. 60/772,193, filed Feb. 10, 2006, U.S. Provisional Application No. 60/772,111, filed Feb. 10, 2006, U.S. Provisional Application No. 60/772,120, filed Feb. 10, 2006, U.S. Provisional Application No. 60/772,110, filed Feb. 10, 2006, U.S. Provisional Application No. 60/772,112, filed Feb. 10, 2006, U.S. Provisional Application No. 60/846,948, filed Sep. 25, 2006, U.S. Provisional Application No. 60/853,920, filed Oct. 24, 2006, U.S. Provisional Application No. 60/859,264, filed Nov. 15, 2006, U.S. Provisional Application No. 60/872,705, filed Dec. 4, 2006, U.S. Provisional Application No. 60/880,824, filed Jan. 17, 2007 and is a continuation of U.S. patent application Ser. No. 11/705,312 the disclosures of which are expressly incorporated herein by reference in their entirety.

FIELD OF THE INVENTION

This invention relates to detergent compositions comprising conjugate esters of 1,3-propanediol. Specifically, the invention relates to detergent compositions comprising conjugate esters of biologically-derived 1,3-propanediol.

BACKGROUND OF THE INVENTION

For many solutions, crèmes and soft solids the active ingredient is only a small portion of the product. Much of these products are composed of other ingredients, adjuvants, which provide benefit to the product. These adjuvants convey benefit to the product in a variety of ways. Some adjuvants allow the active ingredient to be applied in a particular manner, by changing or assisting to change the concentration, feel or viscosity of the solution. Such classes of this type of adjuvants are emulsifiers, conditioners, surfactants, structurants, and thickeners. Other adjuvants protect the active ingredient or the product as whole from disintegrating from its desired form. Humectants, temperature stabilizers and chemical stabilizers are classes of this type of adjuvant. Still other adjuvants provide an aesthetic appeal to the appearance of product. Adjuvants of this type can be further classified as opacifiers, colorants or pearlizing agents,

Many different substances have been experimented with for their ability to act as an adjuvant of one type or another, even to fulfill multiple roles. Both naturally occurring substances and chemically synthesized substances have been experimented with. For instance, waxes, oils, alcohols, fatty acids, petroleum products, esters, salts and polymers have all been used in the past. However, to this date there is a desire for an adjuvant that can be used in various roles and is created in a manner that is pleasing to the consumer.

Consumers and manufacturers are increasingly concerned with the environmental impact of all products. The effort towards environmental impact awareness is a universal concern, recognized by government agencies. The Kyoto Protocol amendment to the United Nations Framework Convention on Climate Change (UNFCCC) currently signed by 156 nations is one example of a global effort to favor safer environmental manufacturing over cost and efficiency. Consumers are increasingly selective about the origins of the products they purchase. The 2004 Co-operative Bank's annual Ethical Consumerism Report (www.co-operativebank.co.uk) disclosed a 30.3% increase in consumer spending on ethical retail products (a general classification for environmental safe, organic and fair trade goods) between 2003 and 2004 while total consumer spending during the same period rose only 3.7%.

One of the single greatest environmental concerns to consumers is the global warming effect and greenhouse gases that contribute to the effect. Greenhouse gases are gases that allow sunlight to enter the atmosphere freely. When sunlight strikes the Earth's surface, some of it is reflected back towards space as infrared radiation. Greenhouse gases absorb this infrared radiation and trap the heat in the atmosphere. Over time, the amount of energy sent from the sun to the Earth's surface should be about the same as the amount of energy radiated back into space, leaving the temperature of the Earth's surface roughly constant. However, increasing the quantity of greenhouse gases above the quantity that existed before the rise of human industrialization is thought to increase the retained heat on the Earth's surface and produce the global warming observed in the last two centuries.

Carbon dioxide is singled out as the largest component of the collection of greenhouse gases in the atmosphere. The level of atmospheric carbon dioxide has increased 50% in the last two hundred years. Any further addition of carbon dioxide to the atmosphere is thought to further shift the effect of greenhouse gases from stabilization of global temperatures to that of heating. Consumers and environmental protection groups alike have identified industrial release of carbon into the atmosphere as the source of carbon causing the greenhouse effect. Only organic products composed of carbon molecules from renewably based sources such as plant sugars and starches and ultimately atmospheric carbon are considered to not further contribute to the greenhouse effect, when compared to the same organic molecules that are petroleum or fossil fuel based.

In addition to adding carbon dioxide to the atmosphere, current methods of industrial production of propanediols produce contaminants and waste products that include among them sulfuric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, tartaric acid, acetic acids, alkali metals, alkaline earth metals, transitional metals and heavy metals, including iron, cobalt, nickel, copper, silver, molybdenum, tungsten, vanadium, chromium, rhodium, palladium, osmium, iridium, rubidium, and platinum (U.S. Pat. Nos. 2,434,110, 5,034,134, 5,334,778, and 5,10,036).

There is a need for all manufactures to provide products reduced environmental impacts, and to especially consider the carbon load on the atmosphere. There is also an environmental advantage for manufacturers to provide products of renewably based sources.

Published U.S. Patent Application No. 2005/0069997 discloses a process for purifying 1,3-propanediol from the fermentation broth of a cultured E. coli that has been bioengineered to synthesize 1,3-propanediol from sugar. The basic process entails filtration, ion exchange and distillation of the fermentation broth product stream, preferably including chemical reduction of the product during the distillation procedure. Also provided are highly purified compositions of 1,3-propanediol.

SUMMARY OF THE INVENTION

A detergent composition comprising a 1,3-propanediol ester and a hydrotrope is provided. The detergent composition can further comprise a surfactant, or a glycol component. Detergent compositions comprising a glycol component can have 1,3-propanediol as the glycol component.

Also provided is a process for producing a detergent composition comprising an ester of 1,3-propanediol, and the 1,3-propanediol is biologically-derived. The process comprises providing 1,3-propanediol with at least 90% biobased carbon, contacting the 1,3-propanediol with an organic acid, forming the ester, recovering the ester, and incorporating the ester into a detergent composition.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is diagram of nuclear magnetic resonance spectra of the products obtained in Example 3. The figure plots the following values: (CDCl₃): δ=0.88 (t, CH ₃—CH₂, 6H), 1.26 (t, CH₂—CH ₂—CH₂, 28H), 1.61 (t, CH ₂—CH₂—C═O, 4H), 1.97 (t, —O—CH₂—CH ₂—CH₂—O, 2H), 2.28 (t, CH ₂—C═O, 4H), 4.15 (t, C(═O)—O—CH ₂— 4H).

FIG. 2 is a DSC (Differential Scanning Calorimetry) curve of the product obtained in Example 3. DSC (Tm=66.4° C. and Tc=54.7° C.).

FIG. 3 is diagram of nuclear magnetic resonance spectra of the products obtained in example 4. The figure plots the following values: δ□=0.88 (t, CH ₃—CH₂, 6H), 1.26 (t, CH₂—CH ₂—CH₂, 28H), 1.61 (t, CH ₂—CH₂—C═O, 4H), 1.97 (t, —O—CH₂—CH ₂—CH₂—O, 2H), 2.28 (t, CH ₂—C═O, 4H), 4.15 (t, C(═O)—O—CH ₂— 4H).

FIG. 4 is diagram of nuclear magnetic resonance spectra of the recrystallized products obtained in example 5. The figure plots the following values: δ□=0.88 (t, CH ₃—CH₂), 1.27 (t, CH₂—CH ₂—CH₂), 1.60 (t, CH ₂—CH₂—C═O), 1.87 and 1.96 (t, —O—CH₂—CH ₂—CH₂—O,), 2.31 (t, CH ₂—C═O,), 3.70 (t, HO—CH ₂—CH₂—), 4.15 and 4.24 (t, C(═O)—O—CH ₂—).

Figure is diagram of nuclear magnetic resonance spectra of the products obtained in example 6. The figure plots the following values: δ□=0.88 (t, CH ₃—CH₂), 1.27 (t, CH₂—CH ₂—CH₂), 1.63 (t, CH ₂—CH₂—C═O), 1.82, 1.87 and 1.96 (t, —O—CH₂—CH ₂—CH₂—O,), 2.31 (t, CH ₂—C═O,), 3.69 and 3.86 (t, HO—CH ₂—CH₂—), 4.15 and 4.21 (t, C(═O)—O—CH ₂—).

FIG. 6 is diagram of nuclear magnetic resonance spectra of the products obtained in example 7. The figure plots the following values: δ□=0.88 (t, CH ₃—CH₂), 1.27 (t, CH₂—CH ₂—CH₂), 1.60 (t, CH ₂—CH₂—C═O), 1.87 and 1.96 (t, —O—CH₂—CH ₂—CH₂—O,), 2.31 (t, CH ₂—C═O,), 3.70 (t, HO—CH ₂—CH₂—), 4.15 and 4.24 (t, C(═O)—O—CH ₂—).

FIG. 7 is diagram of nuclear magnetic resonance spectra of the products obtained in example 8. The figure plots the following values: δ□=0.88 (t, CH ₃—CH₂), 1.27 (t, CH₂—CH ₂—CH₂), 1.63 (t, CH ₂—CH₂—C═O), 1.82, 1.87 and 1.96 (t, —O—CH₂—CH ₂—CH₂—O,), 2.31 (t, CH ₂—C═O,), 3.70 and 3.86 (t, HO—CH ₂—CH₂—), 4.15 and 4.24 (t, C(═O)—O—CH ₂—).

BIOLOGICAL DEPOSITS

The transformed E. coli DH5α containing cosmid pKP1 containing a portion of the Klebsiella genome encoding the glycerol dehydratase enzyme was deposited on 18 Apr. 1995 with the ATCC under the terms of the Budapest Treaty and is identified by the ATCC number ATCC 69789. The transformed E. coli DH5α containing cosmid pKP4 containing a portion of the Klebsiella genome encoding a diol dehydratase enzyme was deposited on 18 Apr. 1995 with the ATCC under the terms of the Budapest Treaty and is identified by the ATCC number ATCC 69790. As used herein, ‘ATCC’ refers to the American Type Culture Collection international depository located at 10801 University Boulevard, Manassas, Va., 20110-2209, U.S.A. The “ATCC No.” is the accession number to cultures on deposit with the ATCC.

DETAILED DESCRIPTION OF THE INVENTION

Applicants specifically incorporate the entire content of all cited references in this disclosure. Further, when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.

Conjugate esters of 1,3-propanediol are suitable, in a non-limiting way, for use in the composition of liquid soaps and liquid detergents as emulsifiers, pearlizing agents, surfactants, gelling agents, structurant, thickener, or opacifiers. The esters described herein are especially desirable as components of detergent formulations as they provide the intended functionality and can be produced from a biologically-derived compound.

Fatty acid monoesters and diesters of biologically-produced 1,3 propanediol are formed by esterification of biologically derived 1,3-propanediol. Biologically-derived 1,3-propanediol can be obtained through catalytic conversion of non-fossil fuel carbon via fermentation with an organism that is able to synthesize 1,3-propanediol. The process provides 1,3-propanediol and its conjugate monoesters and diesters without introducing additional carbon into the atmosphere during the production, use, or disposal of the material.

Biologically produced 1,3 propanediol represents a new feedstock for useful monoesters and diesters of 1,3 propanediol. Such monoesters and diesters have not previously been produced from a biosourced monomer. As such, new compositions of matter, comprising 1,3 propanediol esters derived from biosourced carbon substrates are provided. These compositions may be distinguished from similar compositions derived from all petrochemical carbon on the basis of biobased carbon content.

The terms used in this application shall be accorded the following definitions:

The terms “bio-PDO esters”, “bio-based PDO ester”, “biologically-derived-PDO esters” and “biologically-based 1,3-propanediol esters” and similar terms as used herein refer to monoesters and diesters produced from biologically produced 1,3-propanediol.

The terms “bioPDO”, “bio-produced PDO”, “biologically-produced 1,3-propanediol”, “bio-derived 1,3-propanediol” and “biologically derived 1,3-propanediol” and similar terms as used here in refer to 1,3-propanediol derived from microorganism metabolism of plant-derived sugars composed of carbon of atmospheric origin, and not composed of fossil-fuel carbon.

“Substantially purified,” as used by applicants to describe the biologically-produced 1,3-propanediol produced by the process of the invention, denotes a composition comprising 1,3-propanediol having at least one of the following characteristics: 1) an ultraviolet absorption at 220 nm of less than about 0.200 and at 250 nm of less than about 0.075 and at 275 nm of less than about 0.075; or 2) a composition having L*a*b* “b*” color value of less than about 0.15 and an absorbance at 270 nm of less than about 0.075; or 3) a peroxide composition of less than about 10 ppm; or 4) a concentration of total organic impurities of less than about 400 ppm.

A “b*” value is the spectrophotometrically determined “Yellow Blue measurement as defined by the CIE L*a*b* measurement ASTM D6290.

The abbreviation “AMS” refers to accelerator mass spectrometry.

“Biologically produced” means organic compounds produced by one or more species or strains of living organisms, including particularly strains of bacteria, yeast, fungus and other microbes. “Bio-produced” and biologically produced are used synonymously herein. Such organic compounds are composed of carbon from atmospheric carbon dioxide converted to sugars and starches by green plants.

“Biologically-based” means that the organic compound is synthesized from biologically produced organic components. It is further contemplated that the synthesis process disclosed herein is capable of effectively synthesizing other monoesters and diesters from bio-produced alcohols other than 1,3-propanediol; particularly including ethylene glycol, diethylene glycol, triethylene glycol, -, dipropylene diol, tripropylene diol, 2-methyl 1,3-propanediol, neopentyl glycol and bisphenol A. “Bio-based”, and “bio-sourced”; “biologically derived”; and “bio-derived” are used synonymously herein.

“Fermentation” as used refers to the process of metabolizing simple sugars into other organic compounds. As used herein fermentation specifically refers to the metabolism of plant derived sugars, such sugar are composed of carbon of atmospheric origin.

“Carbon of atmospheric origin” as used herein refers to carbon atoms from carbon dioxide molecules that have recently, in the last few decades, been free in the earth's atmosphere. Such carbons in mass are identifiable by the present of particular radioisotopes as described herein. “Green carbon”, “atmospheric carbon”, “environmentally friendly carbon”, “life-cycle carbon”, “non-fossil fuel based carbon”, “non-petroleum based carbon”, “carbon of atmospheric origin”, and “biobased carbon” are used synonymously herein.

“Carbon of fossil origin” as used herein refers to carbon of petrochemical origin. Such carbon has not been exposed to UV rays as atmospheric carbon has, therefore masses of carbon of fossil origin has few radioisotopes in their population. Carbon of fossil origin is identifiable by means described herein. “Fossil fuel carbon”, “fossil carbon”, “polluting carbon”, “petrochemical carbon”, “petro-carbon” and carbon of fossil origin are used synonymously herein.

“Naturally occurring” as used herein refers to substances that are derived from a renewable source and/or are produced by a biologically-based process.

“Fatty acid” as used herein refers to carboxylic acids that are often have long aliphatic tails, however, carboxylic acids of carbon length 4-40 are specifically included in this definition for the purpose of describing the present invention. “Fatty acid esters” as used herein are esters, which are composed of such, defined fatty acids

“Catalyst” as used herein refers to a substance that is facilitates a chemical reaction without being either a reactant or a product of said reaction.

By the acronym “NMR” is meant nuclear magnetic resonance.

By the terms “color” and “color bodies” is meant the existence of visible color that can be quantified using a spectrocolorimeter in the range of visible light, using wavelengths of approximately 400-800 nm, and by comparison with pure water. Reaction conditions can have an important effect on the nature of color production. Examples of relevant conditions include the temperatures used, the catalyst and amount of catalyst While not wishing to be bound by theory, we believe color precursors include trace amounts of impurities comprising olefinic bonds, acetals and other carbonyl compounds, peroxides, etc. At least some of these impurities may be detected by such methods as UV spectroscopy, or peroxide titration.

“Color index” refers to an analytic measure of the electromagnetic radiation-absorbing properties of a substance or compound.

“Hydrogenation reactor” refers to any of the known chemical reactors known in the literature, including but not limited to shaker-tubes, batch autoclaves, slurry reactors, up-flow packed bed, and trickle flow packed bed reactors.

The abbreviation “IRMS” refers to measurements of CO2 by high precision stable isotope ratio mass spectrometry.

The term “carbon substrate” means any carbon source capable of being metabolized by a microorganism wherein the substrate contains at least one carbon atom.

Unless otherwise stated, all percentages, parts, ratios, etc., are by weight. Trademarks are shown in upper case. Further, when an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed.

A small amount of the carbon dioxide in the atmosphere is radioactive. This 14C carbon dioxide is created when nitrogen is struck by an ultra-violet light produced neutron, causing the nitrogen to lose a proton and form carbon of molecular weight 14 which is immediately oxidized in carbon dioxide. This radioactive isotope represents a small but measurable fraction of atmospheric carbon. Atmospheric carbon dioxide is cycled by green plants to make organic molecules during the process known as photosynthesis. The cycle is completed when the green plants or other forms of life metabolize the organic molecules producing carbon dioxide which is released back to the atmosphere. Virtually all forms of life on Earth depend on this green plant production of organic molecule to produce the chemical energy that facilitates growth and reproduction. Therefore, the 14C that exists in the atmosphere becomes part of all life forms, and their biological products. These renewably based organic molecules that biodegrade to CO2 do not contribute to global warming as there is no net increase of carbon emitted to the atmosphere. In contrast, fossil fuel based carbon does not have the signature radiocarbon ratio of atmospheric carbon dioxide.

Assessment of the renewably based carbon in a material can be performed through standard test methods. Using radiocarbon and isotope ratio mass spectrometry analysis, the biobased content of materials can be determined. ASTM International, formally known as the American Society for Testing and Materials, has established a standard method for assessing the biobased content of materials. The ASTM method is designated ASTM-D6866.

The application of ASTM-D6866 to derive a “biobased content” is built on the same concepts as radiocarbon dating, but without use of the age equations. The analysis is performed by deriving a ratio of the amount of radiocarbon (14C) in an unknown sample to that of a modern reference standard. The ratio is reported as a percentage with the units “pMC” (percent modern carbon). If the material being analyzed is a mixture of present day radiocarbon and fossil carbon (containing no radiocarbon), then the pMC value obtained correlates directly to the amount of Biomass material present in the sample.

The modern reference standard used in radiocarbon dating is a NIST (National Institute of Standards and Technology) standard with a known radiocarbon content equivalent approximately to the year AD 1950. AD 1950 was chosen since it represented a time prior to thermo-nuclear weapons testing which introduced large amounts of excess radiocarbon into the atmosphere with each explosion (termed “bomb carbon”). The AD 1950 reference represents 100 pMC.

“Bomb carbon” in the atmosphere reached almost twice normal levels in 1963 at the peak of testing and prior to the treaty halting the testing. Its distribution within the atmosphere has been approximated since its appearance, showing values that are greater than 100 pMC for plants and animals living since AD 1950. It's gradually decreased over time with today's value being near 107.5 pMC. This means that a fresh biomass material such as corn could give a radiocarbon signature near 107.5 pMC.

Combining fossil carbon with present day carbon into a material will result in a dilution of the present day pMC content. By presuming 107.5 pMC represents present day biomass materials and 0 pMC represents petroleum derivatives, the measured pMC value for that material will reflect the proportions of the two component types. A material derived 100% from present day soybeans would give a radiocarbon signature near 107.5 pMC. If that material was diluted with 50% petroleum derivatives, it would give a radiocarbon signature near 54 pMC.

A biomass content result is derived by assigning 100% equal to 107.5 pMC and 0% equal to 0 pMC. In this regard, a sample measuring 99 pMC will give an equivalent biobased content result of 93%.

Assessment of the materials described herein were done in accordance with ASTM-D6866. The mean values quoted in this report encompasses an absolute range of 6% (plus and minus 3% on either side of the biobased content value) to account for variations in end-component radiocarbon signatures. It is presumed that all materials are present day or fossil in origin and that the desired result is the amount of biobased component “present” in the material, not the amount of biobased material “used” in the manufacturing process.

Compositions in accordance with the invention include a composition comprising an ester of 1,3-propanediol. The esters can have a varying amount of biobased carbon depending on the compound used in the esterification. Biologically derived 1,3-propanediol contains biobased carbon. All three carbon atoms in 1,3 propanediol are biobased carbons. If the conjugate esters are formed using carboxylic acids that contain all biobased carbon, then the resulting esters also contain all biobased carbon. If, however, the carboxylic acids contain non-biobased carbons, i.e. carbons from a fossil fuel source, then the resulting ester will contain a percentage of biobased carbon in proportion to the number of carbons contributed from the carboxylic acid compared to the three carbons contributed from the biologically-derived 1,3-propanediol.

For example, distearate propanediol contains 39 carbon atoms, 18 from each of the stearic acid carbon chains and three from the 1,3-propanediol. Accordingly, if the stearic acid is non-biobased, 36 carbons out of the total 39 in distearate propanediol are non-biobased carbon. The predicted theoretical biobased content of distearate propanediol made from biologically-derived propanediol, and non-biologically derived stearic acid is approximately 7.7 percent.

In an analysis performed using the ASTM-D6866 method, propylene glycol dibenzoate (BENZOFLEX® 284, Velsicol Chem. Corp. Rosemont, Ill.) was found to have 0% bio-based carbon content. The same analysis of propanediol dibenzoate, synthesized using biologically-derived 1,3-propanediol had 19% bio-based carbon content. The predicted bio-based carbon content propanediol dibenzoate made from biologically-derived 1,3 propanediol is 17.6%, which is within the standard deviation of the method.

If the stearic acid in the above example is biobased, the resulting distearate propanediol would have a biobased content of 100%. Accordingly, the conjugate esters of biologically-derived 1,3-propanediol have biobased content values proportional to the biobased content of the acids used to form the esters. The esters therefore can have biobased content of at least 3% biobased carbon, at least 6% biobased carbon, at least 10% biobased carbon, at least 25% biobased carbon, at least 50% biobased carbon, at least 75% biobased carbon, and 100% biobased carbon.

If the organic acid is steric acid or oleic acid, the ester recovered should be greater than 5% biobased carbon. When the organic acid is lauric acid, the ester recovered should be greater than 10% biobased carbon.

Biologically-Derived 1,3-Propanediol

Biologically-derived 1,3-propanediol is collected in a high purity form. Such 1,3-propanediol has at least one of the following characteristics: 1) an ultraviolet absorption at 220 nm of less than about 0.200 and at 250 nm of less than about 0.075 and at 275 nm of less than about 0.075; or 2) a composition having L*a*b* “b*” color value of less than about 0.15 and an absorbance at 270 nm of less than about 0.075; or 3) a peroxide composition of less than about 10 ppm; or 4) a concentration of total organic impurities of less than about 400 ppm. A “b*” value is the spectrophotometrically determined Yellow Blue measurement as defined by the CIE L*a*b* measurement ASTMA D6290.

The level of 1,3-propanediol purity can be characterized in a number of different ways. For example, measuring the remaining levels of contaminating organic impurities is one useful measure. Biologically-derived 1,3-propanediol can have a purity level of less than about 400 ppm total organic contaminants; preferably less than about 300 ppm; and most preferably less than about 150 ppm. The term ppm total organic purity refers to parts per million levels of carbon-containing compounds (other than 1,3-propanediol) as measured by gas chromatography.

Biologically-derived 1,3-propanediol can also be characterized using a number of other parameters, such as ultraviolet light absorbance at varying wavelengths. The wavelengths 220 nm, 240 nm and 270 nm have been found to be useful in determining purity levels of the composition. Biologically-derived 1,3-propanediol can have a purity level wherein the UV absorption at 220 nm is less than about 0.200 and at 240 nm is less than about 0.075 and at 270 nm is less than about 0.075.

Biologically-derived 1,3-propanediol can have a b* color value (CIE L*a*b*) of less than about 0.15.

The purity of biologically-derived 1,3-propanediol compositions can also be assessed in a meaningful way by measuring levels of peroxide. Biologically-derived 1,3-propanediol can have a concentration of peroxide of less than about 10 ppm.

It is believed that the aforementioned purity level parameters for biologically-derived and purified 1,3-propanediol (using methods similar or comparable to those disclosed in U.S. Patent Application No. 2005/0069997) distinguishes such compositions from 1,3-propanediol compositions prepared from chemically purified 1,3-propanediol derived from petroleum sources.

1,3-propanediol produced biologically via fermentation is known, including in U.S. Pat. No. 5,686,276, U.S. Pat. No. 6,358,716, and U.S. Pat. No. 6,136,576, which disclose a process using a recombinantly-engineered bacteria that is able to synthesize 1,3-propanediol during fermentation using inexpensive green carbon sources such as glucose or other sugars from plants. These patents are specifically incorporated herein by reference. Biologically-derived 1,3-propanediol can be obtained based upon use of the fermentation broth generated by a genetically-engineered Escherichia coli (E. coli), as disclosed in U.S. Pat. No. 5,686,276. Other single organisms, or combinations of organisms, may also be used to biologically produce 1,3-propanediol, using organisms that have been genetically-engineered according to methods known in the art. “Fermentation” refers to a system that catalyzes a reaction between substrate(s) and other nutrients to product(s) through use of a biocatalyst. The biocatalysts can be a whole organism, an isolated enzyme, or any combination or component thereof that is enzymatically active. Fermentation systems useful for producing and purifying biologically-derived 1,3-propanediol are disclosed in, for example, Published U.S. Patent Application No. 2005/0069997 incorporated herein by reference.

Biologically derived 1,3-propanediol contains carbon from the atmosphere incorporated by plants, which compose the feedstock for the production of biologically derived 1,3-propanediol. In this way, the biologically derived 1,3-propanediol contains only renewable carbon, and not fossil fuel based, or petroleum based carbon. Therefore the use of biologically derived 1,3-propanediol and its conjugate esters has less impact on the environment as the 1,3-propanediol does not deplete diminishing fossil fuels. The use of biologically derived 1,3-propanediol and its conjugate esters also does not make a net addition of carbon dioxide to the atmosphere, and thus does not contribute to greenhouse gas emissions. Accordingly, the present invention can be characterized as more natural and having less environmental impact than similar compositions comprising petroleum based glycols.

Moreover, as the purity of the biologically derived 1,3-propanediol utilized in the food compositions described herein is higher than chemically synthesized 1,3-propanediol and other glycols, risk of introducing impurities that may be unacceptable in food applications is reduced by its use over commonly used glycols, such as propylene glycol.

In one embodiment of the invention, a composition comprising 1,3-propanediol and an ester of 1,3-propanediol is provided, where the 1,3-propanediol is biologically derived. The biologically-derived 1,3-propanediol in these compositions can have at least 85% biobased carbon, at least 95% biobased carbon, or 100% biobased carbon, when assessed by the application of ASTM-D6866 as described above.

A sample of biologically-derived 1,3-propanediol was analyzed using ASTM method D 6866-05. The results received from Iowa State University demonstrated that the above sample was 100% bio-based content. In a separate analysis, also performed using a ASTM-D6866 method, chemical, or petroleum-based 1,3-propanediol (purchased from SHELL) was found to have 0% bio-based content. Propylene glycol (USP grade from ALDRICH) was found to have 0% bio-based content.

It is contemplated herein that other renewably-based or biologically-derived glycols, such as ethylene glycol or 1,2 propylene glycol, diethylene glycol, triethylene glycol among others, can be used in the personal care compositions of the present invention.

There may be certain instances wherein a personal care compositions composition of the invention may comprise a combination of a biologically-derived 1,3-propanediol and one or more non biologically-derived glycol components, such as, for example, chemically synthesized 1,3-propanediol. In such occasions, it may be difficult, if not impossible to determine which percentage of the glycol composition is biologically-derived, other than by calculating the bio-based carbon content of the glycol component. In this regard, in the personal care compositions of the invention, the 1,3-propanediol use to form 1,3 propanediol esters, can comprise at least about 1% blo-based carbon content up to 100% bio-based carbon content, and any percentage there between.

Ester Conjugates of Biologically Derived 1,3-Propanediol

Esters of biologically derived 1,3-propanediol, “bio-PDO” can be synthesized by contacting bio-PDO with an organic acid. The organic acid can be from any origin, preferably either a biosource or synthesized from a fossil source. Most preferably the organic acid is derived from natural sources or bio-derived having formula R1-COOH. Where in the substituent R1 can be saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic, linear or branched hydrocarbon having chain length 1 to 40 or their salts or alkyl esters. The hydrocarbon chain can also have one or more functional groups such as alkene, amide, amine, carbonyl, carboxylic acid, halide, hydroxyl groups. Naturally occurring organic acids produced esters containing all biobased carbon. These naturally occurring organic acids, especially those produced by a biological organism, are classified as bio-produced and the resulting ester or diester could thereby also be classified as bio-produced. Naturally occurring sources of such fatty acids include coconut oil, various animal tallows, lanolin, fish oil, beeswax, palm oil, peanut oil, olive oil, cottonseed oil, soybean oil, corn oil, rape seed oil. Conventional fractionation and/or hydrolysis techniques can be used if necessary to obtain the fatty acids from such materials.

Appropriate carboxylic acids for producing esters of biologically-derived 1,3-propanediol generally include: (1) C1-C3 carbon containing mono carboxylic acids, including formic acid and acetic acid; (2) fatty acids, such as those acids containing four or more carbon atoms; (3) saturated fatty acids, such as butyric acid, caproic acid, valeric acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid; (4) unsaturated fatty acids, such as oleic acid, linoleic acid, and euricic acid; (5) polyunsaturated fatty acids, such as alpha-linolenic acid, stearidonic acid (or moroctic acid), eicosatetraenoic acid, omega-6 fatty acids, arachidonic acids, and omege-3 fatty acids, eicosapentaenoic acid (or timnodonic acid), dosocapentaenoic acid (or clupanodonic acid), and docosahexaenoic acid (or cervonic acid); (6) hydroxy fatty acids, such as 2-hydroxy linoleic acid, and recinoleic acid; phenylalkanoic fatty acids, such as 11-phenyl undecanoic acid, 13-phenyl tridecanoid acid, and 15-phenyl tridecanoid acid; and (7) cyclohexyl fatty acids, such as 11-cyclohexyl undecanoic acid, and 13-cyclohexyl tridecanoic acid.

The following acids and their salts or alkyl esters are specifically useful, acetic, alginic, butyric, lauric, myristic, palmitic, stearic, arachidic, adipic, benzoic, caprylic, maleic, palmitic, phthalic, sebacic, archidonic, erucic, palmitoleic, pentadecanoic, heptadecanoic, nondecanoic, octadectetraenoic, eicosatetraenoic, eicosapentaenoic, docasapentaenoic, tetracosapentaenoic, tetrahexaenoic, docosahexenoic, (alpha)-linolenic, docosahexaenoic, eicosapentaenoic, linoleic, arachidonic, oleic, erucic, formic, propionic, valeric, caproic, capric, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, tartaric, citric, salicylic, acetyl-salicylic, pelargonic, behenic, cerotic, margaric, montanic, melissic, lacceroic, ceromelissic, geddic, ceroplastic undecylenic, ricinoleic, and elaeostearic acid as well as mixtures of such acids. A more preferred list of suitable organic acids are acetic, adipic, benzoic, maleic, sebacic, and mixtures of such acids. A more preferred list of suitable “fatty acids” meaning generally acids named containing 8-40 carbon in the carbon useful in the present invention include butyric, valeric, caproic, caprylic, pelargonic, capric, lauric, myristic, palmitic, stearic, arachidic, behenic, cerotic, oleic, linoleic, linolenic, margaric, montanic, melissic, lacceroic, ceromelissic, geddic, ceroplastic and the mixtures of such acids. Among those acids, these acids, and their salts and alkyl esters are most preferred stearic, lauric, palmetic, oleic, 2-ethyl hexanoic, and 12-hydroxystearic and mixtures of such acids.

The esters produced include all the appropriate conjugate mono and diesters of 1,3 propanediol using the described organic acids. Some esters in particular that are produced include propanediol distearate and monostearate, propanediol dilaurate and monolaurate, propanediol dioleate and monooleate, propanediol divalerate and monovalerate, propanediol dicaprylate and monocaprylate, propanediol dimyristate and monomyristate, propanediol dipalmitate and monopalmitate, propanediol dibehenate and monobehenate, propanediol adipate, propanediol maleate, propanediol dibenzoate, propanediol diacetate, and all mixtures thereof.

In particular, the esters produced include: propanediol distearate and monostearate, propanediol dioleate and monooleate, propanediol dicaprylate and monocaprylate, propanediol dimyristate and monomyristate, propanediol diphthalate and monophthalate, and all mixtures thereof.

Generally 1,3-propanediol can be contacted, preferably in the presence of an inert gas reacted with a fatty acid or mixture of fatty acids or salts of fatty acids in the absence or presence of a catalyst or mixture of two or more catalysts, at temperatures ranging from 25° C. to 400° C.

During the contacting, water is formed and can be removed in the inert gas stream or under vacuum to drive the reaction complete. Any volatile byproducts can be removed similarly. When the reaction is complete, the heating can be stopped and cooled.

The catalyst can be removed preferably by dissolving and removing in deionized water. If catalyst can be removed by treating with deionized water, the reaction mixture is treated with aqueous solutions of acid or base to forms salts and removing the salts either by washing or filtering.

Further purification to obtain high purity fatty esters, preferably for pharmaceutical application can be carried out by dissolving in a solvent that dissolves fatty ester easily at higher temperatures and least at lower temperatures and recrystallyzing with or without addition of additional solvent at low temperatures.

The catalyst can be an acid for non-limiting examples, sulfuric acid, or p-toluene sulfonic acid. The catalyst can also be a base, for non-limiting example, sodium hydroxide. The catalyst can also be a salt, for non-limiting example, potassium acetate. The catalyst can also be an alkoxide, for non-limiting example, titanium tetraisopropoxide. The catalyst can also be a heterogeneous catalyst, for non-limiting examples: zeolite, heteropolyacid, amberlyst, or ion exchange resin. The catalyst can also be a metal salt, for non-limiting examples, tin chloride, or copper chloride, The catalyst can also be an enzyme, such as those known in the art. The catalyst can also be an organic acid, for a non-limiting example, formic acid. Finally the catalyst can also be an organometallic compound, for non-limiting example, n-butylstannoic acid.

This process can be carried out in the presence or absence of a solvent. If a solvent is not necessary to facilitate the production of fatty ester, it is preferred that the process is carried out in the absence of solvent.

The process can be carried out at atmospheric pressure or under vacuum or under pressurized conditions.

Where R1 and R2 is a hydrocarbon, preferably with a carbon chain length of about 1 to about 40. Such hydrocarbons can be saturated or unsaturated, substituted or unsubstituted, linear, branched, cyclic or aromatic.

M is hydrogen, an alkali metal or an alkyl group.

Where R1 is a hydrocarbon, preferably with a carbon number of about 1 to about 40. Such hydrocarbons can be saturated or unsaturated, substituted or unsubstituted, linear, branched, cyclic or aromatic. M is hydrogen, an alkali metal or an alkyl group.

Compositions in accordance with the invention comprise esters in which R1 has one or more functional groups selected from the group consisting of alkene, amide, amine, carbonyl, carboxylic acid, halide, hydroxyl groups, ether, alkyl ether, sulfate and ethersulfate. The esters can have the formula R1—C(═O)—O—CH2-CH2-CH2-O—C(═O)—R2, wherein both R1 and R2 are linear or branched carbon number between about 1 an about 40. R1 and R2 can have one or more functional groups selected from the group consisting of alkene, amide, amine, carbonyl, carboxylic acid, halide, hydroxyl groups, ether, alkyl ether, sulfate and ethersulfate. Additionally, R1 and R2 can be the same carbon chain in the case of a diester.

Any molar ratio of diol to carboxylic acid or its salt or its ester can be used. The preferred range of the diol to carboxylic acid is from about 1:3 to about 2:1. This ratio can be adjusted to shift the favor of the reaction from monoester production to diester production. Generally, to favor the production of diesters slightly more than about a 1:2 ratio is used; whereas to favor the production of monoesters about a 1:1 ratio is used. In general, if the diester product is desired over the monoester the ratio of diol to dicarboxylic acid can range from about 1.01:2 to about 1.1:2; however if the monoester is desired a range of ratios from about 1.01:1 to about 2:1 is used.

The catalyst content for the reaction can be from 1 ppm to 60 wt % of the reaction mixture, preferably from 10 ppm to 10 wt %, more preferably from 50 ppm to 2 wt % of the reaction mixture.

The product may contain diesters, monoesters or combination diesters and monoesters and small percentage of unreacted acid and diol depending on the reaction conditions. Unreacted diol can be removed by washing with deionized water. Unreacted acid can be removed by washing with deionized water or aqueous solutions having base or during recrystallization.

Any ester of 1,3-propanediol can be made or used in accordance with the present invention. Short, middle and long chain monoesters and diesters of the 1,3-propanediol can be made. Specifically those acids containing between about 1 and about 36 carbons in the alkyl chain can be produced. More specifically, the following monoesters and diesters can be produced: propanediol distearate (monostearate and the mixture), propanediol dilaurate (monolaurate and the mixture), propanediol dioleate (monooleate and the mixture), propanediol divalerate (monovalerate and the mixture), propanediol dicaprylate (monocaprylate and the mixture), propanediol dimyristate (monomyristate and the mixture), propanediol dipalmitate (monopalmitate and the mixture), propanediol dibehenate (monobehenate and the mixture), propanediol adipate, propanediol maleate, propanediol dibenzoate, and propanediol diacetate.

Compositions comprising an ester of 1,3-propanediol, wherein the 1,3-propanediol is biologically derived contain biobased carbon from the biologically derived 1,3-propanediol. Accordingly, these esters can have varying amounts of biobased carbon, depending on what acids are used in the esterification process. The compositions can include esters that have at least 1% biobased carbon, at least 3% biobased carbon, at least 6% biobased carbon, at least 10% biobased carbon, at least 25% biobased carbon, at least 50% biobased carbon, at least 75% biobased carbon, or 100% biobased carbon depending on the length of the carbon chain of the organic acid used to produce the ester, whether the ester is a diester or a monoester, and whether the organic acid contained biobased carbon or fossil-fuel based carbon.

These compositions comprising an ester of 1,3-propanediol can be produced by providing biologically produced 1,3-propanediol; contacting the 1,3-propanediol with an organic acid, wherein the ester is produced; and recovering the ester. The 1,3-propanediol provided can have at least 90% biobased carbon, at least 95% biobased carbon, or 100% biobased carbon. Additionally, the biologically-produced 1,3-propanediol provided for the process can have at least one of the following characteristics: 1) an ultraviolet absorption of less than about 0.200 at 220 nm and less than about 0.075 at 250 nm and less than about 0.075 at 275 nm; 2) a composition having L*a*b* “b*” color value of less than about 0.15 and an absorbance of less than about 0.075 at 270 nm; 3) a peroxide composition of less than about 10 ppm; and 4) a concentration of total organic impurities of less than about 400 ppm.

The ester can also be produced by providing 1,3-propanediol with at least 90% biobased carbon; contacting the 1,3-propanediol with an acid, forming the ester; and recovering the ester. The contacting of the 1,3-propanediol with an acid can be done in the presence of a catalyst to facilitate the esterification reaction, and the catalyst can be categorized as a member of one or more of the acids, bases, salts, alkoxides, heterogeneous, catalysts, metal salts, enzymes, organic acids, and organometallic compounds. Specifically, the catalyst can be sulfuric acid, or p-toluene sulfonic acid, sodium hydroxide, potassium acetate, titanium tetraisopropoxide, zeolite, heteropolyacid, amberlyst, ion exchange resin, tin chloride, or copper chloride, formic acid, or n-butylstannoic acid.

The detergent compositions according to the invention comprise a 1,3-propanediol ester and a hydrotrope. The compositions can further comprise a surfactant. In another embodiment, the detergent compositions include a glycol component, and the glycol component can be 1,3-propanediol, among others. The detergent compositions can also include water.

When the detergent compositions include 1,3-propanediol, the 1,3 propanediol can be biologically produced through a fermentation process. In this embodiment, the 1,3-propanediol can have at least 90% biobased carbon, at least 95% biobased carbon, or 100% biobased carbon.

The 1,3-propanediol esters in the detergent compositions can have at least 3% biobased carbon, at least 6% biobased carbon, at least 10% biobased carbon, at least 25% biobased carbon, at least 50% biobased carbon, or 100% biobased carbon.

The detergent compositions can include between about 0.1% to about 50% 1,3 propanediol ester. In other embodiments, the compositions can have between about 0.1% to about 15% 1,3 propanediol ester, between about 0.3% to about 5% 1,3 propanediol ester, between about 5% to about 30% 1,3 propanediol ester, between about 30% to about 60% 1,3 propanediol ester, or between about 60% to about 80% 1,3 propanediol ester.

The 1,3 propanediol esters can be included in detergent compositions for a variety of purposes. These esters operate as hydrotropes, staibilizers, builders, emulisifers, conditioners, pearlizing agents, surfactants, gelling agents, structurants, thickeners, and opacifiers, depending on the specific formulation.

Other components used in conjunction with 1,3 propanediol esters includes diamines, which are useful in improving cleaning performance; surfactants, which improve cleaning performance; glycols, which enhance physical and enzymatic stability; hydrotropes, which serve as phase stabilizers; suds stabilizers, which extend suds volume and duration; builders, which support detergent action; enzymes, which improve cleaning performance; buffers, which serve to adjust the pH; alkali inorganic salts, which support detergent action; perfumes, which remove iron and manganese.

Some appropriate detergent compositions include liquid soaps, liquid detergents, household cleaning products, and industrial cleaning products. Some specific detergents that are appropriate for use with 1,3-propanediol esters include hand dish-washing detergents, machine dish-washing detergents, solid block detergents, solid laundry detergents, liquid laundry detergents, light-duty liquid detergents, heavy-duty liquid detergents, organic or inorganic clothing softeners, laundry bar soaps, and car wash detergents.

Also provided is a process for producing a detergent composition comprising an ester of 1,3-propanediol, where the 1,3-propanediol is biologically-derived. This process includes: providing 1,3-propanediol with at least 90% biobased carbon and contacting the 1,3-propanediol with an organic acid, which forms the ester. The ester is then recovered and incorporated into a detergent composition.

Forms of Detergent Compositions

The detergent compositions containing esters of 1,3-propanediol can take a variety of physical forms including granular, gel, tablet, bar and liquid forms. These compositions include a so-called concentrated granular detergent composition adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.

Exemplary detergents include, but are not limited to, hand dish-washing detergents; machine dish-washing detergents, including solid block detergents; solid laundry detergents, liquid laundry including light-duty liquid detergents (LDLD) and heavy-duty liquid detergents (HDLD); organic or inorganic clothing softeners, laundry bar soaps and car wash detergent, among others.

The detergent compositions of the invention can comprise any form known or used in the art, such as powders, liquids, granules, gels, pastes, tablets, small bags, bars, and double-partitioned containers, sprays or foamed detergents and other homogenous or multi-phase daily detergent product forms. The products can be manually used or coated, and/or can be used in a constant or freely variable amount of use, or by automatic charge means, or can be used in electric products such as washing machines. These products can have a wide range of pH of, e.g., from 2 to 12 or more, and several tens gram-equivalent, per 100 g of the formulation, of NaOH may be added. These products can have a wide range of preliminary alkalinity. Both high suds and low suds detergents are included.

Light-Duty Liquid Detergents (LDLD) compositions include LDLD compositions containing magnesium ions for improving surface activity and/or organic diamines and/or various foam stabilizers and/or suds boosters, such as amine oxides and/or skin feeling improvers of surfactant and relaxing agents and/or enzyme types including protease, and/or sterilizers.

Heavy-Duty Liquid Detergents (HDLD) compositions include all of so-called “structured” or multi-phase and “non-structured” or isotropic liquid types, and generally include aqueous or non-aqueous bleaching agents, and/or enzymes, or do not include bleaching agents and/or enzymes.

Heavy-duty granular detergents (HDGD) compositions include both of a so-called “compact” or coagulated, or non-spray dried type and a so-called “flocculated” or spray dried type. These compositions include both of a phosphate addition type and a phosphate non-addition type. Such detergents can include a type comprising a more general anionic surfactant as a substrate, or may be a so-called “highly nonionic surfactant” type comprising a generally nonionic surfactant held on an absorbent, for example, in or on the surface of a zeolites or other porous inorganic salt.

Softener (STW) compositions include various types of granular or liquid products that are softened by laundry, and can generally include organic (such as quaternary) or inorganic (such as clay) softeners.

Bar Soap (BS & HW) compositions include laundry bars and include both of a type comprising a synthetic detergent and a soap as substrates and a type containing a softener. Such compositions include compositions manufactured by general soap manufacture techniques, such as pressure molding, or techniques that are no so general, such as casting and absorption of surfactant into a porous support. Other hand wash detergents are also included.

Fabric softeners (FS) include both of the conventional liquid and concentrated liquid types and kinds to be added by dryers or supported by a substrate. Other fabric softeners include those that are solid.

Special purpose cleaners (SPC) including the following products are also considered detergents for purposes of this invention: house-hold dry detergent modes, pre-treatment products of laundry bleaching agents, pre-treatment products for fabric protection, liquid higher fabric detergent types, especially high suds products, liquid bleaching agents including both of chlorine type and oxygen bleaching agent type, disinfectants, detergent aids, pre-treatment types including, for example, bleaching additives and “stain-stick” or special sudsing type cleaners, and anti-fading treatment by sunlight.

Specialty household cleanser (SHC) including the following products are also considered detergents for the purposes of this invention: all purpose cleansing in the form of creams, gels, liquids, and floor cleaners; all-purpose sprays such as for cleaning glass surfaces; wipes including all-purpose wipes, glass cleaners, floor cleaners and disinfectants; bathroom, shower and toilet cleaners; mildew cleaners and bleach.

Detergent Components

Detergent compositions of the invention can contain from 0.01 to 99% by weight of one or more of any of the following general auxiliary components: builders, surfactants, enzymes, polymers, bleaching agents, bleach surfactants, catalyst components, various active components or special components such as dispersant polymers, color speckles, silver protecting agents, anti-fogging agents and/or corrosion inhibitors, dyes, fillers, sterilizers, alkaline agents, hydrotropic agents, antioxidants, enzyme stabilizers, pro-perfumes, perfumes, plasticizers, carriers, processing aids, pigments, and solvents for liquid formulations.

In general, detergent components are included for converting a composition containing only the minimum essential components into a composition useful for the desired detergent purpose. It is recognized that those skilled in the art can readily determine which detergent components are required for desired detergent applications.

The precise nature of these additional components, and levels of incorporation thereof, will vary depending upon the physical form of the composition and the nature of the cleaning operation for which it is to be used.

Detergent Surfactants

The detergent compositions of the invention may contain any known detergent surfactant, and such surfactants are well known to those having skill in the art. Specifically, detergent surfactants of the invention can include anionic, nonionic, zwitter-ionic or amphoteric, betaine, and diamine are, surfactants that are known to be useful in detergent applications.

In all of the detergent surfactants, the chain length of the hydrophobic moiety is typically in the general range of from C8 to C20, and especially in the case of laundering with cold water, the chain length is often preferably in the range of from C8 to C18.

Detergent Enzymes

The detergent composition of the invention may use enzymes for various purposes such as removal of protein-based, carbohydrate-based, or triglyceride-based soils from substrates, transfer inhibition of refugee dyes in fabric laundering, and fabric restoration. “Detergent enzymes” as used herein mean all enzymes having advantageous effects in washing, soil removal, and others in laundering.

Builders

Builder compositions are preferably those that control the hardness of minerals in washing water, especially Ca and/or Mg, thus simplifying the removal and/or dispersal of granular soils from the surface, while also optionally imparting an alkaline agent and/or buffering action. In granular or powder detergents, the builder may function as an absorbent for the surfactant. Alternatively, some compositions can be formulated in a completely water-soluble form, which may be either organic or inorganic, depending on the intended utility.

Suitable silicate builders include water-soluble types and hydrated solid types, and include other kinds such as those having a chain, layer or steric structure, amorphous solid silicates, and those as prepared such that they are used as not particularly structured liquid detergents.

Aluminosilicate builders, so-called zeolites, are particularly useful in granular detergents, but can be incorporated into pastes or gels. The aluminosilicates may be crystalline or amorphous, or may be natural or synthetic.

For the purpose of making it easy to control the hardness of minerals in the washing water, especially Ca and/or Mg, or of making it easy to remove granular solids from the surface, the composition of the invention may optionally contain detergent builders in place of or in addition to the foregoing silicates and aluminosilicates. The builders can be made to function in various mechanisms so as to form soluble or insoluble complexes with mineral ions by ion exchange or by providing mineral ions with the surface more adherent than the surface of the material to be cleaned. The amount of the builder can be varied widely depending on the final utility and physical form of the composition.

Here, suitable builders can be selected from the group consisting of phosphates and polyphosphates, especially sodium salts, carbonates, bicarbonates, sodium carbonate, organic mono-, di-, tri-, and tetracarboxylates, especially water-soluble non-surfactant carboxylates in acid, sodium, potassium or alkanolammonium forms, and aliphatic and aromatic type-containing oligomers or water-soluble low-molecular polymer carboxylates. For example, for the purpose of pH buffer, these builders can be complemented by all of fillers or carriers that are important in the techniques of detergent compositions including borates or sulfates, especially sodium sulfate, and other stabilized surfactants and/or builders.

In the invention, builder mixtures can be used. In general, the builder mixture optionally comprises two or more usual builders, and is complemented by a chelating agent, a pH buffer, or a filler.

Examples of phosphorus-containing builders include polyphosphates, represented by tripolyphosphates, pyrophosphates, and glassy polymer metaphosphates, of alkali metals and ammonium and alkanolammoniums, and phosphonates.

Suitable carbonate builders include carbonates of an alkaline earth metal or an alkali metal, inclusive of carbonate minerals such as sodium bicarbonate and sodium carbonate, complex salts of sodium carbonate or potassium carbonate, and calcium carbonate.

As described herein, the “organic detergent builders” suitable for the use along with the alkylaryl sulfonate surfactant include polycarboxylate compounds including water-soluble non-surfactant dicarboxylates and tricarboxylates. More generally, the builder polycarboxylate has plural carboxylate groups, preferably at least three carboxylates. The carboxylate builder can be incorporated in an acidic or partially neutral, neutral or excessively basic form. In the case of the salt form, salts of alkali metals such as sodium, potassium, and lithium, or alkanolammonium salts are preferred. The polycarboxylate builder includes ether polycarboxylates.

Nitrogen containing builders including amino acids such as lysine, or lower alcohol amines like mono, di-, and tri-ethanolamine, try(hydroxymethyl)amino methane, 2-amino-2-methylpropanol, and disodium glutamate.

Citric acid salts such as citric acid and soluble salts thereof are a polycarboxylate builder important for, for example, heavy-duty liquid detergents (HDL) because they are available from resources that can be regenerated and are biodegradable. The citric acid salts can also be used in granular compositions especially in combination of zeolites and/or layered silicates. Oxydisuccinic acid salts are especially useful in such compositions and combinations.

In the detergent composition of the invention, any builders known in this field can be incorporated generally in an amount of from about 0.1 to about 50% by weight, more preferably 0.5 to 30% by weight and most preferably 1 to 25% by weight.

Oxygen Bleaching Agents:

In one embodiment, the invention comprises an “oxygen bleaching agent” as a part or whole of the detergent composition. Any known oxidizing agents can be used. Alternatively, oxidizing agent bleaching agents such as systems of generating hydrogen peroxide by oxygen or an enzyme, or hypohalogenic acid salts, for example, chlorine bleaching agents such as hyposulfites, can also be used.

Examples of peroxide-based general oxygen bleaching agents include hydrogen peroxide, inorganic peroxohydrates, organic peroxohydrates, and organic peroxy acids including hydrophilic or hydrophobic mono- or di-peroxy acids. These components may be peroxycarboxylic acids, perpoxyimide acids, amidoperoxycarboxylic acids, or salts thereof including their calcium, magnesium or mixed cationic salts. Various kinds of peracids can be used in a liberated form or as precursor materials called “bleach surfactant” or “bleach promoters”, which release peracids corresponding to hydrolysis in the case of a combination with a supply source of hydrogen peroxide.

Inorganic peroxides, suproxides, organic hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide, and inorganic peroxo acids and salts thereof, such as peroxosulfates, are also useful as the oxygen bleaching agent.

Mixed oxygen bleaching agent systems are generally effective as in mixtures of oxygen bleaching agents with known bleach surfactant, organic catalysts, enzyme catalysts, or mixtures thereof. Further, these mixtures can further contain brighteners, light bleaching agents, and dye transfer inhibitors of types that are well known in this field.

Hydroperoxides and peroxohydrates are organic salts, or more generally, inorganic salts that can readily release hydrogen peroxide. The peroxohydrates are a general example of a “hydrogen peroxide source” and include perborates, percarbonates, perphosphates, and persilicates. Preferred peroxohydrates include all of sodium carbonate hydroperoxide and equivalent commercially available “percarbonate” bleaching agents, and so-called sodium perborate hydrates, and sodium pyrophosphate hydroperoxide can also be used. Urea hydroperoxides are also useful as the peroxohydrate.

There are included inorganic peroxohydrates, organic peroxohydrates, hydrophilic or hydrophobic mono- or diperacids, organic peracids including peroxycarboxylic acids, peroxyimide acids, and amidoperoxycarboxylic acids, salts of calcium, magnesium, or mixed cationic salts.

In the detergent composition of the invention, any oxygen bleaching agents are added in such formulations preferably in ranges from about 0 to 15%, and most preferably from about 0.2 to 12%

Bleach Surfactant can be used as well. Examples of useful bleach surfactants include amides, imides, esters, and acid anhydrides. Mixtures of bleach surfactants can be also used. The bleach surfactant can be used in an amount of up to 20% by weight, and preferably from 0.1 to 10% by weight of the composition For the form of highly concentrated bleaching agent additive products or the form in which the bleach surfactant is used in an automatic charge device, it can be used in an amount of 40% by weight or more.

Transition Metal Bleaching Agent Catalysts can also be used in the invention. For example, manganese compounds can be optionally used as the bleaching compound to have a catalytic action. As useful cobalt bleaching catalysts, ones that are known may be used.

In addition to the above-enumerated bleach surfactant, Enzyme-Based Supply Sources of Hydrogen Peroxide. For instance, suitable hydrogen peroxide generating mechanisms include combinations of C1 to C4 alkanol oxidases and C1 to C4 alkanols, especially a combination of methanol oxidase (MOX) and ethanol. Bleaching-related other enzymatic materials such as peroxidases, haloperoxidases, and oxidases, superoxide molecular displacement enzymes, catalases, and their reinforcing agents, or more generally, inhibitors can be optionally used in the composition.

Oxygen Transfer Agents and Precursors

All known organic bleaching agent catalysts, oxygen transfer agents, or precursors thereof are also useful herein. These materials include their compounds themselves and/or precursors thereof, such as all of ketones suitable for manufacture of dioxiranes, and and/or dioxirane precursors or all different atom-containing analogues of dioxiranes. As preferred examples of such components, are especially included hydrophilic or hydrophobic ketones that manufacture the dioxiranes on the spot, along with monoperoxysulfate. Examples of such oxygen bleaching agents that are preferably used along with the oxygen transfer agent or precursor include percarboxylic acids and salts, percarbonic acids and slats, peroxy monosulfuric acid and salts, and mixtures thereof.

Polymeric Soil Releasing Agents

The composition of the invention can optionally comprise one or more soil releasing agents. The polymeric soil releasing agent is characterized by having hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of the laundry cycle to function as an anchor for the hydrophilic segments. This can enable stains occurring sequent to treatment with the soil releasing agent to be more easily cleaned in later washing procedures.

In the case of the use, the soil releasing agent generally accounts for from about 0.01 to about 10% by weight of the composition.

Clay Soil Removal/Anti-Redeposition Agents

The composition of the invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines, and liquid detergent compositions typically contain about 0.01% to about 5% by weight of the water-soluble ethoxylated amines.

Preferred soil release and anti-redeposition agents are ethoxylated tetraethylenepentamine. Other preferred soil release removal/anti-redeposition agents are ethoxylated amine polymers, zwitter-ionic polymers, and amine oxides. Other soil release removal and/or anti-redeposition agents that are known in this field can also be used in the composition of the invention. Another type of the preferred anti-redeposition agent includes carboxy methyl cellulose (CMC)-based components.

Polymeric Dispersing Agents

Polymeric dispersing agents can be effectively used in an amount of from about 0.01 to about 10% by weight of the composition of the invention especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release, peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid forms. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, and methylenemalonic acid.

Polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers that are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form range from about 1,000 to 500,000, preferably from about 2,000 to 250,000, and more preferably from about 3,000 to 100,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.

Acrylic acid/maleic acid-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 3,000 to 80,000, and most preferably from about 4,000 to 70,000. The ratio of acrylate to maleate segments in such copolymers generally ranges from about 9:1 to about 1:9, and more preferably from about 8:2 to 3:7. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.

Copolymers of acrylic acid and/or maleic acid and a polyalkylene glycol can also be used as a preferred component of the dispersing/anti-redeposition agent. The copolymers are preferably graft polymers of acrylic acid and/or maleic acid and a polyalkylene glycol, copolymers of acrylic acid and/or maleic acid and an alkylene oxide adduct of allyl alcohol or isoprenol, and copolymers of acrylic acid and/or maleic acid and a polyalkylene glycol acrylate or methacrylate, and more preferably graft polymers of acrylic acid and/or maleic acid and a polyalkylene glycol and copolymers of acrylic acid and/or maleic acid and an alkylene oxide adduct of allyl alcohol or isoprenol.

The average molecular weight of the copolymers preferably ranges from about 2,000 to 100,000, more preferably from about 3,000 to 80,000, and most preferably from about 4,000 to 70,000.

Acrylic acid/acrylamide based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent. The average molecular weight of such copolymers in the acid form preferably ranges from about 3,000 to 100,000, more preferably from about 4,000 to 20,000, and most preferably from about 4,000 to 10,000. The acrylamide content in such copolymers generally is less than about 50%, preferably less than about 20%, and most preferably about 1 to about 15%, by weight of the polymer.

Another polymeric component that can be incorporated is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance as well as act as a clay soil removal/anti-redeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, and more preferably from about 1,500 to about 10,000.

Polyasparatate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolites builders. Dispersing agents such as polyasparatate preferably have a (weight average) molecular weight of about 10,000.

In the detergent compositions according to the invention, polymeric dispersing agents known in this field can be incorporated generally in an amount of from about 0.01 to about 15%, more preferably from 0.05 to 10%, then most preferably 0.1 to 5%.

Brighteners

In the detergent compositions according to the invention, any optical brighteners or other brightening or whitening agents known in this field can be incorporated generally in an amount of from about 0.01 to about 1.2% by weight. Such optical brighteners are often used in the case where the detergent is designed for fabric washing or processing applications.

Polymeric Dye Transfer Inhibiting Agents

The composition of the invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamide N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents generally comprise from about 0.01 to about 10% by weight, preferably from about 0.01 to about 5% by weight, and more preferably from about 0.05 to about 2% by weight of the composition.

The optical brightener selected for use in the invention exhibits especially effective dye transfer inhibition performance benefits when used in combination with the polymeric dye transfer inhibiting agent. The combination of such selected polymeric materials with such selected optical brightener provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone.

Chelating Agents

The detergent compositions according to the invention may also optionally contain one or more chelating agents, especially chelating agents for transition metal coming from others. The transition metals generally seen in washing solutions include water-soluble, colloidal or granular iron and/or manganese and may sometimes associate as oxides or hydroxides. Preferred chelating agents are chelating agents that effectively inhibit such transition metals, especially inhibit such transition metals or their compounds to adhere to fabrics, and/or inhibit non-preferred redox reaction occurred in the washing medium and/or on the interface of the fabric or hard surface. The general chelating agents can be selected from the group consisting of amino carboxylates, amino phosphates, polyfunctionally-substituted aromatic chelating agents, and mixtures thereof.

The compositions according to the invention may also contain water-soluble methyl glycine diacetic acid salts as a chelating agent that can effectively be used together with insoluble builders such as zeolites and layered silicates. If utilized, the chelating agent generally accounts for from about 0.1 to about 15% by weight of the composition. More preferably, if utilized, the chelating agent accounts for from about 0.1 to about 3.0% by weight.

Suds Suppressors

In the case where washing is required in intended utilities, especially washing by washing machines, compounds for reducing or suppressing the formation of suds can be incorporated into the composition of the invention. For other compositions, for example, compositions as designed for hand washing, high sudsing may be desired, and such components can be omitted. Suds suppression can be of particularly importance in the so-called “high concentration cleaning process” and in front-loading European-style washing machines (so-called drum type washing machines).

A very wide variety of materials may be used as suds suppressors. The composition of the invention generally comprises from 0% by weight to about 10% by weight of suds suppressors.

Fabric Softeners

Various through-the-wash fabric softeners can optionally be used in an amount of from about 0.5 to about 10% by weight to provide fabric softener benefits concurrently with fabric cleaning. Clay softeners can be used in combination with amine and cationic softeners. Further, in the cleaning process of the invention, known fabric softeners including those of biodegradation type can be used in modes including the pre-treatment, main cleaning, post-laundry, and addition into washing machines and dryers.

Perfumes

Perfumes and perfumery ingredients useful in the compositions and processes comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, and esters. Also, included are various natural extracts and essences that can comprise complex mixtures of ingredients such as orange oil, lemon, oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, and cedar. Finished perfumes typically comprise from about 0.01 to about 2% by weight of the detergent composition, and individual perfumery ingredients can comprise from about 0.0001 to about 90% by weight of a finished perfume composition.

Other Components

A wide variety of other ingredients useful in detergent compositions can be included in the composition, including other ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, and soil fillers for bar compositions. If high sudsing is desired, suds boosters such as C10 to C16 alkanolamides can be incorporated into the composition, typically in an amount of from 1% by weight to 10% by weight C10 to C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing adjuvant surfactants such as the amine oxides, betaines and sultanines noted above is also advantageous. If desired, water-soluble magnesium and/or calcium salts can be added typically in an amount of from 0.1% by weight to 2% by weight, to provide additional suds.

Various detergent ingredients employed in the composition can optionally be further stabilized by absorbing the ingredients onto a porous hydrophobic substrate, then coating the substrate with a hydrophobic coating. Preferably, the detergent ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use, the detergent ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detergent function.

The liquid detergent composition can contain water and other solvents as diluents. Low-molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for stabilizing the surfactant, but polyols such as those having from 2 to about 6 carbon atoms and from 2 to about 6 hydroxyl groups (such as 1,3-propanediol, ethylene glycol, glycerin, and propylene glycol) can also be used. The composition can contain such diluents in an amount of from 5% by weight to 90% by weight, and preferably from 10% by weight to 50% by weight.

The detergent composition is preferably formulated such that, during use in aqueous cleaning operations, the wash water has a pH of from about 6.5 to about 12.5, preferably from 7 to 12, and more preferably from about 7.0 to about 11. Laundry products are typically at a pH of from 9 to 11. Techniques for controlling the pH at recommended usage levels include the use of buffers, alkalis, and acids.

Liquid Laundry Detergents

While the following listing of ingredients is particularly suited for liquid laundry detergents, it is clearly within the scope of one having skill in the art to determine whether such ingredients may be useful for other detergent applications.

Thickeners

The physical stability of liquid products may be improved and the thickness of the liquid product may be altered by the addition of a cross linking polyacrylate thickener to the liquid detergent product as a thixotropic thickener.

PH Adjusting Components

Liquid detergent products are preferably low foaming, readily soluble in the washing medium and most effective at pH values best conducive to improved cleaning performance, such as in a range of desirably from about pH 6.5 to about pH 12.5, and preferably from about pH 7.0 to about pH 12.0, more preferably from about pH 8.0 to about pH 12.0, and most preferably, less than about 9.0 pH. The pH adjusting components are desirably selected from sodium or potassium hydroxide, sodium or potassium carbonate or sesquicarbonate, sodium or potassium silicate, boric acid, sodium or potassium bicarbonate, sodium or potassium borate, and mixtures thereof. NaOH or KOH are the preferred ingredients for increasing the pH to within the above ranges. Other preferred pH adjusting ingredients are sodium carbonate, potassium carbonate, and mixtures thereof.

Low Foaming Surfactant

The liquid nonionic surfactant detergents that can be used to practice the present invention are preferably are alkyl ethoxylates in non-chlorine bleach liquid ADW compositions. One example of a non-chlorine bleach stable surfactant is SLF18® manufactured by BASF Corporation. Alternatively, in chlorine bleach containing liquid ADW compositions, chlorine bleach stable low foaming surfactants are preferred and such surfactants are present in a range of from about 0.1% to about 10% by weight of the liquid composition. Such surfactants are generally known to one skilled in the art and need not be elaborated here, for purposes of brevity. An example of a chlorine bleach stable surfactant is Dowfax® anionic surfactant available from the Dow Chemical Company.

Examples of the nonionic surfactant include polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, polyoxyalkylene glycerin fatty acid esters, monoglycerides, sorbitan fatty acid esters, fatty acid monoethanolamides, fatty acid diethanolamides and alkyl polyglucosides.

Examples of the amphoteric surfactants include acetic acid betaines, amidoacetic acid betaines, sulfobetaines, amidosulfobetaines, phosphobetaines, alkylamine oxides, and amidoamine oxides. Of these, fatty acid amidopropylbetaines such as cocamidopropyl betaine and lauramidopropyl betaine are preferred. Include imidazoline derived amphoterics: disodium cocoa amphodiproprionate.

Two or more of these surfactants may be used in combination. The surfactant is preferably contained in an amount of from 5 to 50 wt. %, more preferably from 10 to 30 wt. %, even more preferably from 10 to 20 wt. % based on the detergent composition of the present invention, from the viewpoints of foaming property, liquid properties during use and detergency.

Silicones

The detergent composition of the present invention may contain silicones for further improvement in the conditioning effects. The silicones include dimethylpolysiloxanes (viscosity: 5 mm.sup.2/s to 20 million mm.sup.2/s), amino-modified silicones, polyether-modified silicones, methylphenylpolysiloxanes, fatty acid -modified silicones, alcohol-modified silicones, alkoxy-modified silicones, epoxy-modified silicones, fluorine-modified silicones, cyclic silicones and alkyl-modified silicones, of which dimethylpolysiloxanes are preferred. The content of the silicone in the detergent composition of the present invention is preferably from 0.01 to 10 wt. %. The detergent composition of the present invention may contain other conditioning components such as a cationic polymer (cationic cellulose, cationic guar gum, or the like). Their content in the detergent composition of the present invention is preferably from 0.1 to 5 wt. %.

General Liquid Components

The detergent composition of the present invention may contain, in addition, components employed ordinarily for detergent compositions according to the intended use. Examples of such components include humectants such as propylene glycol, glycerin, diethylene glycol monoethyl ether, sorbitol and panthenol; colorants such as dyes and pigments; viscosity regulators such as methyl cellulose, polyethylene glycol and ethanol; plant extracts; antiseptics; bactericides; chelating agents; vitamin preparations; anti-inflammatory agents; perfumes; ultraviolet absorbers; and antioxidants.

Solid Laundry Detergents

While the following listing of ingredients is particularly suited for solid laundry detergents, it is clearly within the scope of one having skill in the art to determine whether such ingredients may be useful for other detergent applications.

Preferably, the detergent composition has a particle size distribution such that no more than 10 wt % by weight of the composition, has a particle size greater than 850 micrometers, and no more than 10 wt % by weight of the composition, has a particle size less than 250 micrometers.

The composition optionally comprises one or more adjunct components. The adjunct components are typically selected from the group consisting of other anionic surfactants, cationic surfactants, non-ionic surfactants, zwitterionic surfactants, other builders, polymeric co-builders such as polymeric polycarboxylates, bleach, other hydrotropes, chelants, enzymes, anti-redeposition polymers, soil-release polymers, polymeric soil-dispersing and/or soil-suspending agents, dye-transfer inhibitors, fabric-integrity agents, fluorescent whitening agents, suds suppressors, fabric-softeners, flocculants, cationic fabric-softening components, perfumes and combinations thereof.

A suitable adjunct component may be an anionic surfactant other than the alkyl alkoxylated sulphate surfactant and the linear alkyl benzene sulphonate surfactant. Suitable other anionic surfactants are branched or linear C₈-C₁₈ alkyl sulphate surfactants. An especially suitable other anionic surfactants are methyl branched C₈-C₁₈ alkyl sulphate surfactants.

A suitable adjunct component may be an anionic surfactant other than the alkyl alkoxylated sulphate surfactant and the linear alkyl benzene sulphonate surfactant. Suitable other anionic surfactants are branched or linear C₈-C₁₈ alkyl sulphate surfactants. An especially suitable other anionic surfactants are methyl branched C₈-C₁₈ alkyl sulphate surfactants.

A suitable adjunct component may be a hydrotrope other than the alkoxylated alkyl alcohol. Suitable hydrotropes include sodium cumene sulphate, sodium toluene sulphate and sodium xylene sulphate.

Gel Detergents

While the following listing of ingredients is particularly suited for gel detergents, it is clearly within the scope of one having skill in the art to determine whether such ingredients may be useful for other detergent applications. The lamellar-phase gel laundry composition of the invention comprises from 1 to 8%, more preferably from 3 to 6%, by weight of a gelling agent.

A fatty alcohol gelling agent can be used, such as 1-decanol, 1-dodecanol, 2-decanol, 2-dodecanol, 2-methyl-1-decanol, 2-methyl-1-dodecanol, 2-ethyl-1-decanol, and mixtures thereof. Commercially available materials that are particularly suitable for use as gelling agent include Neodol 23 or Neodol 25 produced by Shell Chemical Co., Exxal 12 or Exxal 13 produced by Exxonmobil Chemical Co. and Isalchem 123 or Lialchem 123 produced by Sasol Chemical Co.

The gelling agent may also suitably be a non-neutralized fatty acid having the formula R₃—(COOH)—R₄, wherein R₃ and R₄ are independently selected from hydrogen and saturated or unsaturated, linear or branched C₁-C₂₂ alkyl groups, whereby the total number of carbon atoms in the fatty acid is between 10 and 23. Such a fatty acid gelling agent is preferably selected from oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid, linoleic acid, linolenic acid and mixtures thereof.

Furthermore, the gelling agent may suitably be a naturally obtainable fatty acid selected from tallow, coconut, and pal kernel fatty acids.

Anionic Surfactant

The anionic surfactant that may be present in the gel composition of the invention is preferably selected from the group consisting of linear alkyl benzene sulphonates, alkyl sulphonates, alkylpolyether sulphates, alkyl sulphates and mixtures thereof.

Nonionic Surfactant

The surfactant system in the gel composition of the invention may also contain a nonionic surfactant.

Nonionic detergent surfactants are well-known in the art. They normally consist of a water-solubilizing polyalkoxylene or a mono- or d-alkanolamide group in chemical combination with an organic hydrophobic group derived, for example, from alkylphenols in which the alkyl group contains from about 6 to about 12 carbon atoms, dialkylphenols in which primary, secondary or tertiary aliphatic alcohols (or alkyl-capped derivatives thereof), preferably having from 8 to 20 carbon atoms, monocarboxylic acids having from 10 to about 24 carbon atoms in the alkyl group and polyoxypropylene. Also common are fatty acid mono- and dialkanolamides in which the alkyl group of the fatty acidradical contains from 10 to about 20 carbon atoms and the alkyloyl group having from 1 to 3 carbon atoms. In any of the mono- and di-alkanolamide derivatives, optionally, there may be a polyoxyalkylene moiety joining the latter groups and the hydrophobic part of the molecule.

Builders

Builders in this embodiment that may be used according to the present invention include conventional alkaline detergent builders, inorganic or organic, which can be used at levels of from 0% to 50% by weight of the gel composition, preferably from 1% to 35% by weight.

Examples of suitable inorganic detergency builders that may be used are water soluble alkali metal phosphates, polyphosphates, borates, silicates, and also carbonates and bicarbonates. Specific examples of such builders are sodium and potassium triphosphates, pyrophosphates, orthophosphates, hexametaphosphates, tetraborates, silicates, and carbonates.

Examples of suitable organic detergency builders are: (1) water-soluble amino polycarboxylates, e.g. sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(2 hydroxyethyl)-nitrilodiacetates; (2) water-soluble salts of phytic acid, e.g. sodium and potassium phytates; (3) water-soluble polyphosphonates, including specifically sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid; sodium and potassium salts of methylene diphosphonic acid; sodium and potassium salts of ethylene diphosphonic acid; and sodium and potassium salts of ethane-1,1,2-triphosphonic acid.

In addition, polycarboxylate builders can be used satisfactorily, including water-soluble salts of mellitic acid, citric acid, and carboxymethyloxysuccinic acid, salts of polymers of itaconic acid and maleic acid, tartrate monosuccinate, and tartrate disuccinate.

The detergency builder includes carboxylates, polycarboxylates, aminocarboxylates, carbonates, bicarbonates, phosphates, phosphonates, silicates, borates and mixtures thereof.

Amorphous and crystalline zeolites or aluminosilicates can also be suitably used as detergency builder in gel compositions.

Enzymes

Suitable enzymes for use in the detergent compositions of the invention include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof, of any suitable origin, such as vegetable, animal bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity, thermostability, and stability to active bleach detergents, builders and the like. In this respect bacterial and fungal enzymes are preferred such as bacterial proteases and fungal cellulases.

Enzymes are normally incorporated into detergent composition at levels sufficient to provide a “cleaning-effective amount”. The term “cleaning effective amount” refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, or freshness improving effect on the treated substrate. In practical terms for normal commercial operations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of detergent composition. Stated otherwise, the composition of the invention may typically comprise from 0.001 to 5%, preferably from 0.01 to 1% by weight of a commercial enzyme preparation.

Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Higher active levels may be desirable in highly concentrated detergent formulations.

Suitable examples of proteases are the subtilisins that are obtained from particular strains of B. subtilis and B. licheniformis. One suitable protease is obtained from a strain of Bacillis, having maximum activity throughout the pH-range of 8-12, developed and sold as ESPERASE®® by Novozymes of Industries A/S of Denmark.

Other suitable proteases include ALCALASE®, EVERLASE®, LIQUANASE®, and SAVINASE®, and POLARZYME® from Novozymes, from PURAFECT®, and PROPERASE®, from Genencor International and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands.

Suitable lipase enzymes for use in the composition of the invention include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB-1,372,034. A very suitable lipase enzyme is the lipase derived from humicola lanuginosa and available from Novozymes, Denmark Nordisk under the tradename LIPOLASE®. Other suitable lipase enzames are LIPEX® from Novozymes.

Suitable cellulose enzymes for use in the composition of the invention include those produced by microorganism of the Aspergillus sp. Suitable cellulose enzymes are available under tradename CAREZYME®, CELLUZYME®, from Novozymes, PURADAX®, AND PRIMAFAST®LUNA from Genencor International.

Alpha-amylase enzymes can be produced by microorganism of Bacillus sp. and are available under the tradename as TERMAMYL®, STAINZYME®, DURAMYL®, from Novozymes, Denmark. Alpha-amylase enzyme is available as PURASTAR® from Genencor International.

Mannanase enzymes are available under tradename MANNAWAY®, from Novozymes, Denmark and PURABRITE® from Genencor International.

Mixtures or blends of enzymes for use in the compositions of the invention are available under tradename as T-BLEND EVERLASE/DURAMYL/LIPEX®, T-BLEND SAVINASE/CAREZYME®, T-BLEND SAVINASE/LIPEX®, T-BLEND SAVINASE/LIPOLASE®, T-BLEND SAVINASE/STAINZYME®, T-BLEND SAVINASE/TERMAMYL®, T-BLEND SAVINASE/TERMAMYL/CELLUZYME®, from Novozymes, Denmark.

Other Optional Components

In addition to the anionic and nonionic surfactants described above, the surfactant system of the invention may optionally contain a cationic surfactant.

Furthermore, alkaline buffers may be added to the compositions of the invention, including monethanolamine, triethanolamine, borax, and the like.

As another optional ingredient, an organic solvent may suitably be present in the gel composition of the invention, preferably at a concentration of up to 10% by weight.

There may also be included in the formulation, minor amounts of soil suspending or anti-redeposition agents, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose or hydroxy-propyl methyl cellulose.

Optical brighteners for cotton, polyamide and polyester fabrics, and anti-foam agents such as silicone oils and silicone oil emulsions may also be used.

Other optional ingredients which may be added in minor amounts, are soil release polymers, dye transfer inhibitors, polymeric dispersing agents, suds suppressors, dyes, perfumes, colourants, filler salts, antifading agents and mixtures thereof.

Liquid Hand Dishwashing Detergents

While the following listing of ingredients is particularly suited for liquid hand dishwashing detergents, it is clearly within the scope of one having skill in the art to determine whether such ingredients may be useful for other detergent applications.

Anionic Surfactants

Anionic sulfonate surfactants suitable for use herein include the salts of alkylbenzene sulfonates, alkyl ester sulfonates, primary or secondary alkane sulfonates, olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

Anionic sulfate surfactants suitable for use in the compositions of the invention include linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, and alkyl phenol ethylene oxide ether sulfates.

Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps (“alkyl carboxyls”).

Water

Detergent compositions often include water. The proportion of water in the compositions generally is in the range of 35% to 85%, preferably 50% to 80% by weight of the usual composition.

Amine Oxide

Amine oxides useful in the present invention include long-chain alkyl amine oxides, ie., those compounds having the formula:

R³(OR⁴)_(x)—(NO)—(R⁵)₂

wherein R³ is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 16 carbon atoms; R⁴ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof; x is from 0 to 3, preferably 0; and each R⁵ is an alkyl or hydroxyalkyl group containing from 1 to 3, preferably from 1 to 2 carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferably 1, ethylene oxide groups. The R⁵ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include C₁₀-C₁₈ alkyl dimethyl amine oxides and C₈-C₁₂ alkoxy ethyl dihydroxyethyl amine oxides and alkyl amido propyl amine oxide. Examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide, dodecylamidopropyl dimethylamine oxide and dimethyl -2-hydroxyoctadecylamine oxide. Preferred are C₁₀-C₁₈ alkyl dimethylamine oxide, and C₁₀-C₁₈ acylamido alkyl dimethylamine oxide.

Betaine

The betaines useful in the present invention are those compounds having the formula R(R¹)₂ N⁺R² COO⁻ wherein R is a C₆-C₁₈ hydrocarbyl group, preferably C₁₀-C₁₆ alkyl group, each R¹ is typically C₁-C₃, alkyl, preferably methyl, and R² is a C₁-C₅ hydrocarbyl group, preferably a C₁-C₅ alkylene group, more preferably a C₁-C₂ alkylene group. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C₁₂-C₁₄ acylamidopropylbetaine; C₁₂-C₁₈ acylamidohexyldiethyl betaine; 4-[C₁₄-C₁₆ acylmethylamidodiethylammonio]-1-carboxybutane; C₁₆-C₁₈ acylamidodimethylbetaine; C₁₂-C₁₆ acylamidopentanediethyl-betai-ne; C₁₂-C₁₆ acylmethyl-amidodimethylbetaine, and coco amidopropyl betaine. Preferred betaines are C₁₂-C₁₈ dimethylammoniohexanoate and the C₁₀-C₁₈ acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Also included are sulfobetaines (sultaines) of formula R(R₁)₂ N+R₂ SO₃—, wherein R is a C₆-C₁₈ Hydrocarbyl group, preferably a C₁₀-C₁₆ alkyl group, more preferably a C₁₂-C₁₃ alkyl group; each R₁ is typically C₁-C₃ alkyl, preferably methyl and R₂ is a C₁-C₆ hydrocarbyl group, preferably a C₁-C₃ alkylene or, preferably, hydroxyalkylene group. Examples of suitable sultaines are C₁₂-C₁₄ dihydroxyethylammonio propane sulfonate, and C₁₆-C₁₈ dimethylammonio hexane sulfonate, with C₁₂-C₁₄ amido propyl ammonio-2-hydroxypropyl sultaine being preferred.

Alkanolamide Compounds

Detergent compositions can include an alkanolamide compound such as an alkyl monoalkanol amide, an alkyl dialkanol amide, and mixtures thereof.

Detergent formulations include a hydrotrope selected from the group consisting of ethanol, isopropanol, sodium xylene sulfonate, propylene glycol, sodium cumene sulfonate, urea, polyethylene glycol and mixtures thereof.

Solvents

Detergent compositions can include a solvent selected from the group consisting of alcohols (ethanol, isopropanol) glycols (1,3-propanediol, propylene glycol, polyethylene glycol) polyols and polyethers (dipropylene glycol, dipropylene glycol methyl ether), and mixtures thereof.

Inorganic Salt

Detergent compositions can include an inorganic or organic salt or oxide of a multivalent cation, particularly Mg⁺⁺ which has phase stabilization properties. The multivalent cation salt or oxide provides several benefits including improved cleaning performance in dilute usage, particularly in soft water areas, and minimized amounts of perfume required to obtain the microemulsion state. Magnesium sulfate, either anhydrous or hydrated (e.g., heptahydrate), is preferred as the magnesium salt. Good results also have been reported with magnesium oxide, magnesium chloride, magnesium acetate, magnesium propionate and magnesium hydroxide. These magnesium salts can be used with formulations at neutral or acidic pH since magnesium hydroxide will not precipitate at these pH levels.

Although magnesium is the typical cation from which the salts (inclusive of the oxide and hydroxide) are formed, other polyvalent metal ions also can be used provided that their salts are nontoxic and are soluble in the aqueous phase of the system at the desired pH level.

Other Components

The liquid cleaning composition of this invention may, if desired, also contain other optional components either to provide additional effect or to make the product more attractive to the consumer. The following are mentioned by way of example: Colorants or dyes in amounts up to 0.5% by weight; preservatives or antioxidizing agents, such as formalin, 5-bromo-5-nitro-dioxan-1,3; 5-chloro-2-methyl-4-isothaliazolin-3-one, 2,6-di-tert.butyl-p-cresol, etc., in amounts up to 2% by weight; and pH adjusting agents, such as sulfuric acid or sodium hydroxide, as needed. Furthermore, if opaque compositions are desired, up to 4% by weight of an opacifier may be added. Preferably, the optional ingredients are selected from the group consisting of hydrotropes, perfumes, colorants, pH adjusting agents, preservatives, biocidal agents, inorganic salts, opacifiers, viscosity modifiers, and mixtures thereof

Uses of Esters from Bio-Derived 1,3-Propanediol

1,3 propanediol esters as described herein are also suitable, in a non-limiting way, for use in the composition of liquid soaps and liquid detergents as emulisifers, pearlizing agents, surfactants, gelling agents, structurants, thickeners, or opacifiers. The esters containing about 1 to about 24 carbons in the alkyl chain are particularly useful in liquid detergent applications.

Such liquid soaps and liquid detergents can be directs to any animal, especially avians, reptiles and mammals. The preferred applications are directed to humans, canine, feline and equine species. The most preferred applications are directed to human species.

In addition, the esters of the instant application may used for powder detergents, such as powder dishwasher detergent, and textiles detergents.

Such esters are also useful as a solvent in detergents, especially for botanical products. Such detergent compositions comprising botanical products include botanicals directed to plants, their seeds, stems, roots, flowers, leaves, pollen, spices, and oils.

The esters in the detergent compositions described herein may also function as an antimicrobial agent.

A further description of types of detergent formulations comprising fatty acid esters can be found in “Liquid Detergents” (Surfactant Science Series Volume 129, Taylor & Francis Group, Boca Raton, Fla., 2005). Additional description follows, including reference to light-duty and heavy-duty detergents, both of which are the subject of the detergents compositions provided herein.

Light-duty liquid detergents are for dishwashing (by hand) and liquid detergents for textile, delicate garments—usually the exposure times are relatively short, about 20 minutes and the use concentrations are low, about 0.15%. Esters in these compositions provide benefit as non-ionic surfactants.

Heavy-duty liquid detergents (HDLD) are for textile applications (for washing machines). In this context the fatty acid esters are useful as the non-ionic surfactants. The non-ionic surfactants (beside the anionic surfactants) are primarily responsible for wetting the surfaces of fabrics as well as the soil (reducing surface and interfacial tension), helping to lift the stains off the fabric surface, and stabilizing dirt particles and/or emulsifying grease droplets. Esters in these compositions provide additional benefits as aesthetic ingredients and help to create a microemulsion.

General Formulation of a Structured HDLD:

Ingredient Function % Sodium Linear Alkylbenzene Sulfonate Anionic surfactant 0-30 Sodium Alkyl Ether Sulfate Anionic surfactant 0-10 Alcohol Ethoxylate Nonionic surfactant 0-10 Sodium Carbonate Builder 0-25 Zeolite Builder 0-25 Sodium Perborate Bleach 0.0-10.0 Polymer Stabilizer 0.0-1.0  Protease Enzyme 0.0-1.5  Fluorescent Whitening Agent Brightener 0.0-0.5  Boric Acid 0.0-5.0  Preservative 0.05-0.2  Fragrance 0.0-0.6  Colorant 0.00-0.2 

General Formulation of an Unstructured HDLD:

Ingredient Function % Sodium Linear Alkylbenzene Sulfonate Anionic surfactant  0-15 Sodioum Alkyl Ether Sulfate Anionic surfactant  0-15 Alcohol Ethoxylate Nonionic surfactant  0-15 Sodium Citrate Builder  0-10 Monoethanolamine Buffer 0-5 Soap Defoamer 0.0-5   Protease Enzyme 0.0-1.5 Fluorescent Whitening Agent Brightener 0.0-0.5 Boric Acid Enzymer stabilizer 0.0-5.0 Ethanol Solvent 0.0-5   Sodium Xylene Sulfonate Hydrotrope  0.0-10.0 Preservative 0.05-0.2  Fragrance 0.0-0.6 Colorant 0.00-0.2 

Fatty acid esters of 1,3 propanediol can also function as non-ionic cosofteners. Generally glycol fatty acid esters deliver good softness and static control without any drawback.

Other type of detergents within the instant invention include cream cleaners, as fatty acid esters, including esters of 1,3 propanediol, provide microemulsion characteristics that benefit cream cleaners and detergents. Gel cleaners can also be formulated within the esters of 1,3 propanediol for the same reasons.

All of the compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of the present disclosure have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit, and scope of the invention. More specifically, it will be apparent that certain agents, which are chemically related, may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope, and concept of the invention as defined by the appended claims.

Examples

The present invention is further defined in the following Examples. These Examples, while indicating preferred embodiments of the invention, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

The meaning of abbreviations used is as follows: “min” means minute(s), “sec” means second(s), “h” means hour(s), “μL” means microliter(s), “mL” means milliliter(s), “L” means liter(s), “nm” means nanometer(s), “mm” means millimeter(s), “cm” means centimeter(s), “μm” means micrometer(s), “mM” means millimolar, “M” means molar, “mmol” means millimole(s), “μmole” means micromole(s), “g” means gram(s), “μg” means microgram(s), “mg” means milligram(s), “g” means the gravitation constant, “rpm” means revolutions per minute, “SEM” means standard error of the mean, “vol %” means volume percent and “NMR” means nuclear magnetic resonance.

General Methods:

Standard recombinant DNA and molecular cloning techniques used in the Examples are well known in the art and are described by Sambrook, J., Fritsch, E. F. and Maniatis, T., Molecular Cloning: A Laboratory Manual, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y., 1989, by T. J. Silhavy, M. L. Bennan, and L. W. Enquist, Experiments with Gene Fusions, Cold Spring Harbor Laboratory, Cold Spring Harbor, N.Y., 1984, and by Ausubel, F. M. et al., Current Protocols in Molecular Biology, Greene Publishing Assoc. and Wiley-Interscience, N.Y., 1987.

Materials and methods suitable for the maintenance and growth of bacterial cultures are also well known in the art. Techniques suitable for use in the following Examples may be found in Manual of Methods for General Bacteriology, Phillipp Gerhardt, R. G. E. Murray, Ralph N. Costilow, Eugene W. Nester, Willis A. Wood, Noel R. Krieg and G. Briggs Phillips, eds., American Society for Microbiology, Washington, D.C., 1994, or by Thomas D. Brock in Biotechnology: A Textbook of Industrial Microbiology, Second Edition, Sinauer Associates, Inc., Sunderland, Ma., 1989.

All reagents, restriction enzymes and materials used for the growth and maintenance of bacterial cells were obtained from Aldrich Chemicals (Milwaukee, Wisc.), BD Diagnostic Systems (Sparks, Md.), Life Technologies (Rockville, Md.), or Sigma Chemical Company (St. Louis, Mo.), unless otherwise specified.

Glycerol used in the production of 1,3-propanediol was obtained from J. T. Baker Glycerin USP grade, Lot 325608 and G19657.

Differential Scanning Calorimetry. DSC thermograms were recorded using Universal V3 1A TA instrument under constant stream of nitrogen with a heating and cooling rate of 10° C./min.

NMR: 1H NMR spectra were recorded on Bruker DRX 500 using XWINNMR version 3.5 software. Data was acquired using a 90 degree pulse (p1) and a 30 second recycle delay (d1). Samples were dissolved in deuterated chloroform and nondeuterated chloroform was used as internal standard.

Isolation and Identifying Bio-PDO:

The conversion of glycerol to bio-PDO was monitored by HPLC. Analyses were performed using standard techniques and materials available to one of skill in the art of chromatography. One suitable method utilized a Waters Maxima 820 HPLC system using UV (210 nm) and RI detection. Samples were injected onto a Shodex SH-1011 column (8 mm×300 mm, purchased from Waters, Milford, Ma.) equipped with a Shodex SH-1011P precolumn (6 mm×50 mm), temperature controlled at 50° C., using 0.01 N H2SO4 as mobile phase at a flow rate of 0.5 mL/min. When quantitative analysis was desired, samples were prepared with a known amount of trimethylacetic acid as external standard. Typically, the retention times of glycerol (RI detection), 1,3-propanediol (RI detection), and trimethylacetic acid (UV and RI detection) were 20.67 min, 26.08 min, and 35.03 min, respectively.

Production of bio-PDO was confirmed by GC/MS. Analyses were performed using standard techniques and materials available to one of skill in the art of GC/MS. One suitable method utilized a Hewlett Packard 5890 Series II gas chromatograph coupled to a Hewlett Packard 5971 Series mass selective detector (EI) and a HP-INNOWax column (30 m length, 0.25 mm i.d., 0.25 micron film thickness). The retention time and mass spectrum of 1,3-propanediol generated from glycerol were compared to that of authentic 1,3-propanediol (m/e: 57, 58).

Production of Bio-Based Monoesters and Diesters from Bio-Produced 1,3-propanediol

Monoesters and diester of bio-produced 1,3-propanediol may be produced by combining bio-PDO with organic acid. The combination is to be preformed in dry conditions under heat and prolong agitation with a selected catalyst. The ratio of monoester to diester produced will vary according to the molar ratio of acid to bio-PDO and the selection of catalyst.

The production of esters was confirmed using ¹H nuclear magnetic resonance. Analyses were performed using standard techniques and materials available to one of skill in the art of ¹H NMR.

Proton Nuclear Magnetic Resonance (¹H NMR) Spectroscopy is a powerful method used in the determination of the structure of unknown organic compounds. It provides information concerning: the number of different types of hydrogens present in the molecule, the electronic environment of the different types of hydrogens and the number of hydrogen “neighbor” a hydrogen has.

The hydrogens bound to carbons attached to electron withdrawing groups tend to resonate at higher frequencies from TMS, tetramethylsilane, a common NMR standard. The position of where a particular hydrogen atom resonates relative to TMS is called its chemical shift (δ). Typical chemicals shifts of fatty ester are as follows.

-   -   δ==0.88 for terminal CH₃     -   δ=1.26, 1.61 and 1.97 for methylene groups of (—CH₂—CH ₂—CH₂),         (CH ₂—CH₂—C═O) and (O—CH₂—CH ₂—CH₂—O) respectively,     -   δ=2.28 for methylene group adjustcent to ester (CH ₂—C═O)     -   δ=4.15 for ester (C(═O)—O—CH ₂—).         Proton NMR can distinguish the protons corresponding to the end         groups (CH ₂—OH) (δ=3.7) from that of the middle ester groups         (CH ₂—O—C(═O)—) (δ=4.15 and 4.24 for diester and monoester,         respectively) and thus it is possible to identify ester and can         monitor the reaction by comparing the integral areas of these         two peaks.

${\% \mspace{14mu} {Esterification}} = \frac{\begin{matrix} {{Combined}\mspace{14mu} {areas}\mspace{14mu} {of}\mspace{14mu} {peaks}\mspace{14mu} {at}\mspace{14mu} 41.5\mspace{14mu} {and}} \\ {4.24 \times 100} \end{matrix}}{\begin{matrix} {{Combined}\mspace{14mu} {areas}\mspace{14mu} {of}\mspace{14mu} {peaks}{\mspace{11mu} \;}{at}} \\ {3.70,{41.5\mspace{14mu} {and}\mspace{14mu} 4.24}} \end{matrix}}$

Example 1 Conversion of D-Glucose to 1,3-Propanediol Under Fermentation Conditions

E. coli strain ECL707, containing the K. pneumoniae dha regulon cosmids pKP1 or pKP2, the K. pneumoniae pdu operon pKP4, or the Supercos vector alone, is grown in a 5 L Applikon fermenter for the production of 1,3-propanediol from glucose.

The medium used contains 50-100 mM potassium phosphate buffer, pH 7.5, 40 mM (NH4)2SO4, 0.1% (w/v) yeast extract, 10 μM CoCl2, 6.5 μM CuCl2, 100 μM FeCl3, 18μ □M FeSO4, 5 μM H3BO3, 50 μM MnCl2, 0.1 μM Na2MoO4, 25μ M ZnCl2, 0.82 mM MgSO4, 0.9 mM CaCl2, and 10-20 g/L glucose. Additional glucose is fed, with residual glucose maintained in excess. Temperature is controlled at 37° C. and pH controlled at 7.5 with 5N KOH or NaOH. Appropriate antibiotics are included for plasmid maintenance. For anaerobic fermentations, 0.1 vvm nitrogen is sparged through the reactor; when the dO setpoint was 5%, 1 vvm air is sparged through the reactor and the medium is supplemented with vitamin B12.

Titers of 1,3-propanediol (g/L) range from 8.1 to 10.9. Yields of bio-PDO (g/g) range from 4% to 17%.

Example 2 Purification of Biosourced 1,3-Propanediol

1,3-propanediol, produced as recited in Example 1, was purified, by a multistep process including broth clarification, rotary evaporation, anion exchange and multiple distillation of the supernatant.

At the end of the fermentation, the broth was clarified using a combination of centrifugation and membrane filtration for cell separation, followed by ultrafiltration through a 1000 MW membrane. The clarified broth processed in a large rotary evaporator. Approximately 46 pounds of feed material (21,000 grams) were processed to a concentrated syrup. A 60 ml portion of syrup was placed in the still pot of a 1″ diameter distillation column. Distillation was conducted at a vacuum of 25 inches of mercury. A reflux ratio of approximately 1 was used throughout the distillation. Several distillate cuts were taken, the central of which received further processing. The material was diluted with an equal volume of water, the material was loaded onto an anion exchange column (mixed bed, 80 grams of NM-60 resin), which had been water-washed. Water was pumped at a rate of 2 ml/min, with fractions being collected every 9 minutes. Odd number fractions were analyzed, and fractions 3 through 9 contained 3G. The fractions containing 36 were collected and subjected to microdistillation to recover several grams of pure 1,3-propanediol monomer (which was polymerized to mono and diesters according the methods described in Example 2-8).

Example 3 Production of Propanediol Distearate using p-Toluenesulfonic Acid as Catalyst

To prepare propanediol distearate from biosource 1,3-propanediol and stearic acid, bio-source 1,3-propanediol was purified using methods as in examples 1 and 2. 2.58 g (0.033 moles) of bio-source 1,3-propanediol, 19.45 g (0.065 moles) of stearic acid (Aldrich, 95%), and 0.2125 g (0.001 moles) of p-toluenesulfonic acid (Aldrich 98.5%) were charged into glass reactor fitted with mechanical stirrer and the reactor was flushed with dry nitrogen gas to remove air and moisture for 15 min. Then reaction temperature was raised to 100° C. while thoroughly stirring the reaction mixture under nitrogen flow and continued for 210 min.

After completion of the reaction, reaction mixture was cooled to about 35° C. and the product was transferred into a beaker. The product was purified by adding 100 mL of water and thoroughly stirring at 45-60° C., to form an emulsion for 15 min. The mixture was cooled and the solid propanediol distearate was separated by filtration.

The product was characterized by ¹H NMR (Nuclear Magnetic Resonance) spectra (CDCl₃ (deuterated chloroform)): δ=0.88 (t, CH ₃—CH₂, 6H), 1.26 (t, CH₂—CH ₂—CH₂, 28H), 1.61 (t, CH ₂—CH₂—C═O, 4H), 1.97 (t, —O—CH₂—CH ₂—CH₂—O, 2H), 2.28 (t, CH ₂—C═O, 4H), 4.15 (t, C(═O)—O—CH ₂— 4H) and DSC (Tm=66.4° C. and Tc=54.7° C.). FIG. 1 depicts a graph of these data.

Example 4 (or Comparative Example 1) Production of Propanediol Distearate using Chemical 1,3-Propanediol and p-Toluenesulfonic Acid as Catalyst

Chemical 1,3-propanediol (Shell Chemical, LP Houston, Tex.) was prepared as described herein, specifically as described in Examples 1 and 2. 5.2 g (0.068 moles) of 1,3-propanediol, 38.9 g (0.13 moles) of stearic acid (Aldrich, 95%), and 0.425 g (0.002 moles) of p-toluenesulfonic acid (Aldrich, 98.5%) were charged into glass reactor fitted with mechanical stirrer and the reactor was flushed with dry nitrogen gas to remove air and moisture for 15 min. Then reaction temperature was raised to 130° C. while thoroughly stirring the reaction mixture under nitrogen flow and continued for 195 min at 130° C.

The product was purified as described in Example 3. The product was further purified by dissolving in chloroform and recrystallizing by adding acetone at 15° C. The recrystallized product was filtered and dried.

The product was characterized by ¹H NMR spectra (CDCl₃): δ□=0.88 (t, CH ₃—CH₂, 6H), 1.26 (t, CH₂—CH ₂—CH₂, 28H), 1.61 (t, CH ₂—CH₂—C═O, 4H), 1.97 (t, —O—CH₂—CH ₂—CH₂—O, 2H), 2.28 (t, CH ₂—C═O, 4H), 4.15 (t, C(═O)—O—CH ₂— 4H). FIG. 3 depicts a graph of these data.

The NMR spectra of the product was compared to the spectra of product described in Example 5. No differences were found in the chemical structure of the esters synthesized biologically derived and chemically derived 1,3-propanediol.

Example 5 Production of Propanediol Distearate using p-Toluenesulfonic Acid as Catalyst

39.61 g (0.133 moles) of stearic acid (Aldrich, 95%), 5.05 g (0.066 moles) of 1,3-propanediol and 0.46 g (0.0024 moles) of p-toluenesulfonic acid were charged into glass reactor fitted with mechanical stirrer and the reactor was flushed with dry nitrogen gas to remove air and moisture for 15 min. Then reaction temperature was raised to 100° C. while thoroughly stirring the reaction mixture under nitrogen flow. When the reaction temperature reached 100° C., nitrogen flow was shut off and low vacuum was applied to remove by byproduct. The reaction was continued for 2 h. The vacuum was stopped and product was cooled under nitrogen flow.

The product was purified as described in Example 3 and recrystallized as described in Example 4.

The product was characterized by ¹H NMR spectra (CDCl₃): δ□=0.88 (t, CH ₃—CH₂, 6H), 1.26 (t, CH₂—CH2—CH₂, 28H), 1.61 (t, CH ₂—CH₂—C═O, 4H), 1.97 (t, —O—CH₂—CH ₂—CH₂—O, 2H), 2.28 (t, CH ₂—C═O, 4H), 4.15 (t, C(═O)—O—CH ₂— 4H). FIG. 4 depicts a graph of these data.

Example 6 Production of Propanediol Monostearate and Propanediol Distearate using Tin Chloride as Catalyst

72.06 g (0.243 moles) of stearic acid (Aldrich, 95%), 9.60 g (0.126 moles) of 1,3-propanediol and 0.25 g of SnCl₂ (Aldrich 98%) were charged into glass reactor fitted with mechanical stirrer and the reactor was flushed with dry nitrogen gas to remove air and moisture for 15 min. Then reaction temperature was raised to 120° C. while thoroughly stirring the reaction mixture under nitrogen flow and continued for 240 min.

After completion of the reaction, reaction mixture was cooled and analyzed by NMR. The product contained 39 mole % of propanediol monostearate, 19 mole % of propanediol distearate and 42 mole % 1,3-propanediol.

¹H NMR spectra (CDCl₃) δ□=0.88 (t, CH ₃—CH₂), 1.27 (t, CH₂—CH ₂—CH₂), 1.63 (t, CH ₂—CH₂—C═O), 1.82, 1.87 and 1.96 (t, —O—CH₂—CH ₂—CH₂—O,), 2.31 (t, CH ₂—C═O,), 3.69 and 3.86 (t, HO—CH ₂—CH₂—), 4.15 and 4.21 (t, C(═O)—O—CH ₂—). FIG. 5 depicts a graph of these data.

Example 7 Production of Propanediol Monostearate and Propanediol Distearate using Titanium Tetraisopropoxide as Catalyst

35.51 g (0.119 moles) of stearic acid (Aldrich, 95%), 9.55 g (0.125 moles) of 1,3-propanediol and 0.01 g of Ti(OC₃H₇)₄ (Aldrich, 99.99%) were charged into glass reactor fitted with mechanical stirrer and the reactor was flushed with dry nitrogen gas to remove air and moisture for 15 min. Then reaction temperature was raised to 170° C. while thoroughly stirring the reaction mixture under nitrogen flow and continued for 240 min. Then the reaction was continued under vacuum for another 30 min. The vacuum was stopped and product was cooled under nitrogen flow and analyzed by NMR.

The product has 36 mole % propanediol monostearate and 64 mole % propanediol distearate.

¹H NMR spectra (CDCl3) δ□=0.88 (t, CH ₃—CH₂), 1.27 (t, CH₂—CH ₂—CH₂), 1.60 (t, CH ₂—CH₂—C═O), 1.87 and 1.96 (t, —O—CH₂—CH ₂—CH₂—O,), 2.31 (t, CH ₂—C═O,), 3.70 (t, HO—CH ₂—CH₂—), 4.15 and 4.24 (t, C(═O)—O—CH ₂—). FIG. 6 depicts a graph of these data.

Example 8 Production of Propanediol Monostearate and Propanediol Distearate using Potassium Acetate as Catalyst

39.72 g (0.133 moles) of stearic acid (Aldrich, 95%), 10.12 g (0.133 moles) of 1,3-propanediol and 2.47 g (0.025 moles) of potassium acetate (Aldrich, 99%) were charged into glass reactor fitted with mechanical stirrer and the reactor was flushed with dry nitrogen gas to remove air and moisture for 15 min.

Then reaction temperature was raised to 130° C. while thoroughly stirring the reaction mixture under nitrogen flow. The reaction was continued for 4 h under nitrogen flow. Then the nitrogen flow was shut off and vacuum was applied for 10 min before stopping the reaction. The obtained product was analyzed without further purification.

NMR analysis confirmed the product contained 64.7 mole % of propanediol monostearate, 9.7% mole % of Propanediol distearate and 25.6 mole % 1,3 Propanediol.

¹H NMR spectra (CDCl₃) δ=0.88 (t, CH ₃—CH₂), 1.27 (t, CH₂—CH ₂—CH₂), 1.63 (t, CH ₂—CH₂—C═O), 1.82, 1.87 and 1.96 (t, —O—CH₂—CH ₂—CH₂—O,), 2.31 (t, CH ₂—C═O,), 3.70 and 3.86 (t, HO—CH ₂—CH₂—), 4.15 and 4.24 (t, C(═O)—O—CH ₂—). FIG. 7 depicts a graph of these data.

Example 9 Production of Propanediol Dilaurate using p-Toluenesulfonic Acid as Catalyst

50.2 g (0.246 moles) of lauric acid (Aldrich, 98%), 9.35 g (0.123 moles) of 1,3-propanediol and 0.6 g (0.0031 moles) of p-toluenesulfonic acid (Aldrich 98.5%) were charged into glass reactor fitted with mechanical stirrer and the reactor was flushed with dry nitrogen gas to remove air and moisture for 15 min.

Then reaction temperature was raised to 130° C. while thoroughly stirring the reaction mixture under nitrogen flow. The reaction was continued for 4 h under nitrogen flow. After completion of the reaction, the product was cooled and 90 mL of 0.5 wt % sodium hydroxide solution was added and agitated at 40 to 50° C. for 10 min. Then the product was filtered and thoroughly washed with deionized water and dried.

NMR analysis confirmed the product contained 99.2 mole % of propanediol dilaurate

¹H NMR spectra (CDCl₃) δ=0.88 (t, CH ₃—CH₂), 1.27 (t, CH₂—CH ₂—CH₂), 1.63 (t, CH ₂—CH₂—C═O), 1.96 (t, —O—CH₂—CH ₂—CH₂—O,), 2.28 (t, CH ₂—C═O,), 4.15 (t, C(═O)—O—CH ₂—)

Example 10 Production of Propanediol Dioleate using p-Toluenesulfonic Acid as Catalyst

51.7 g (0.164 moles) of oleic acid (Aldrich, 90%), 6.26 g (0.082 moles) of 1,3-propanediol and 0.6 g (0.0031 moles) of p-toluenesulfonic acid (Aldrich 98.5%) were charged into glass reactor fitted with mechanical stirrer and the reactor was flushed with dry nitrogen gas to remove air and moisture for 15 min.

Then reaction temperature was raised to 130° C. while thoroughly stirring the reaction mixture under nitrogen flow. The reaction was continued for 4 h under nitrogen flow. After completion of the reaction, the product was cooled and 90 mL of 0.5 wt % sodium hydroxide solution was added and agitated at 40 to 50° C. for 10 min.

The mixture was transferred into a separating funnel and 500 mL of deionized water added and mixture was allowed to form tow separate layers. Aqueous layer was removed.

Another 500 mL deionized water was added, the solution was mixed and aqueous layer was after two clear layer were formed. The process was repeated for one more time.

NMR analysis confirmed the product contained 99.2 mole % of propanediol dilaurate

¹H NMR spectra (CDCl₃) δ□=0.88 (t, CH ₃—CH₂), 1.27 and 1.30 (CH₂—CH ₂—CH₂), 1.63 (t, CH ₂—CH₂—C═O), 1.96 (t, —O—CH₂—CH ₂—CH₂—O,), 2.28 (t, CH ₂—C═O,), 4.15 (t, C(═O)—O—CH ₂—), 5.35 (m CH2-CH═CH—CH2)

Examples 11—are prophetic and similar to compositions described in the following patents, U.S. Pat. No. 4,620,976; 4,654,163; 6,165,955; 6,417,146 B1; and U.S. Pat. No. 6,894,013 B2, herein specifically incorporated by reference.

Example 11 Detergents Comprising Esters Formed from Biologically Derived 1,3-Propanediol

Fatty acid 1,3 propanediol ester: 5.0-30.0% 1,3 propanediol distearate Fatty acid alkanolamide: 2.0-20.0% Coconut oil acid monoethanolamide Surfactant: 0.1-10.0% Sodium lauryl triglycol ether-sulfosuccinate Coconut-alkyldimethylamine oxide Sodium salt 0.1-3.0%  Mono- or Di-valent Water up to 100.0%

Addition of a fatty acid 1,3 propanediol ester with a fatty acid alkanolamide and an ether-sulfate-free surfactant will yield a pearlescent dispersion having 1) excellent pearlescent effect, 2) good storage ability, and 3) low viscosity. This composition will form a pearlescent dispersion with good flow properties and low surfactant content.

Example 12 Liquid Detergent Comprising Esters Formed from Biologically Derived 1,3-Propanediol

Fatty acid 1,3 propanediol ester: 5.0-30.0% 1,3 propanediol distearate Fatty acid alkanolamide: 2.0-20.0% Cocomonoethanolamide Nonionic surfactant: 0.1-10.0% C₁₀₋₁₂ - Fatty polyol alkyl ester Water up to 100.0%

Addition of a fatty acid 1,3 propanediol ester with a fatty acid alkanolamide and a nonionic surfactant will yield a pearlescent dispersion having 1) excellent pearl luster effect, 2) long shelf life, 3) compatibility with cationic surfactants, 4) resistance to hydrolysis, 5) low viscosity, and 6) reduced foaming.

Example 13 Liquid Detergent Comprising Esters Formed from Biologically Derived 1,3-Propanediol

Fatty acid 1,3 propanediol ester: 5.0-40.0% 1,3 propanediol distearate Nonionic surfactant: 3.0-30.0% Laureth-7 Amphoteric surfactant: 0.0-10.0% Cocoamidopropyl betaine Cocoamphoacetate Glycol: 0.0-15.0% Propylene glycol (1,2 and/or 1,3) Water up to 100.0%

In this composition the fatty acid 1,3 propanediol ester functions as a pearlizing agent, the nonionic surfactant functions as an emulsifier and stabilizer, the amphoteric surfactant functions as a co-emulsifier to enhance pearlizing effect, and the glycol functions as an emulsifier as well.

Example 14 Liquid Detergent Comprising Esters Formed from Biologically Derived 1,3-Propanediol

Fatty acid glycol ester sulfate (A) 10.0-60.0% Propanediol lauric acid sulfate sodium salt Additional surfactant (B) 90.0-40.0% (anionic, nonionic, cationic, amphoteric, and/or zwitterionic) Sodium laureth sulfate Water up to 100.0%

Foaming behavior may be tested by, preparing a 10% by weight aqueous surfactant solution (21° dH+1% by weight sebum) and determining the foam volume by Standard DIN 53902, Part 1. Test solutions can be made using weight ratios of A (10.0-60.0%) and B (90.0-40.0%). The fatty acid glycol ester sulfates may exhibit advantageous properties: 1) foam booster for other surfactants, 2) foam stability in the presence of hard water and/or oil, 3) improve formulation of surfactants with poor solubility in cold water, 4) contribute to cleaning performance, 5) dermatologically safe, 6) readily biodegradable, and 7) free of nitrosamines.

Example 15 Liquid Detergent Comprising Esters Formed from Biologically Derived 1,3-Propanediol

Surfactant: 1.0-50.0% (anionic, nonionic, or amphoteric) Sodium POE (3) lauryl ether sulfate Lauryl amidopropylbetaine Coconut oil fatty acid monothanol amide POE (12) lauryl ether Fatty acid 1,3 propanediol ester: 0.3-5.0%  1,3 propanediol distearate Glyceryl ether 0.1-10.0% N-Octyl glyceryl ether Water up to 100.0%

Compositions using the 1,3 propanediol ester will have a pearly luster, and are excellent in the dispersion stability of a pearlent.

Procedure—combine all ingredients together, heating the mixture to 80° C. and allowing the ingredients to melt, and then cooling the melt to 30° C. with stirring. 

1. A method of reducing the anthropogenic CO₂ emission of a detergent composition upon biodegradation, the method comprising: preparing a detergent composition comprising an ester wherein said ester is a 1,3-propanediol ester, wherein said 1,3-propanediol portion of said ester is biologically-derived, biodegradable, and exhibits no anthropogenic CO₂ emission upon biodegradation, and using said detergent composition whereby said detergent composition biodegrades, wherein said reduction of anthropologic CO₂ emission is compared to the anthropologic CO₂ emission of a detergent composition not comprising an ester wherein said ester is a 1,3-propanediol ester, wherein said 1,3-propanediol portion of said ester is biologically-derived and biodegradable.
 2. The method of claim 1 wherein said detergent composition comprises a solid.
 3. The method of claim 1 wherein said detergent composition comprises a liquid.
 4. The method of claim 1 wherein the ester comprises a biobased content of at least 3% biobased carbon.
 5. The method of claim 1 wherein said ester comprises a biobased content of at least 6% biobased carbon.
 6. The method of claim 1 wherein said ester comprises a biobased content of at least 25% biobased carbon.
 7. The method of claim 1 wherein said ester comprises a biobased content of at least 50% biobased carbon.
 8. The method of claim 1 wherein said ester comprises a biobased content of at least 75% biobased carbon.
 9. The method of claim 1 wherein said ester comprises a radiocarbon signature of at least 3.225 pMC when calculated according to the ASTM-D6866 method.
 10. The method of claim 1 wherein said ester comprises a radiocarbon signature of at least 6.45 pMC when calculated according to the ASTM-D6866 method.
 11. The method of claim 1 wherein said ester comprises a radiocarbon signature of at least 10.75 pMC when calculated according to the ASTM-D6866 method.
 12. The method of claim 1 wherein said ester comprises a radiocarbon signature of at least 26.875 pMC when calculated according to the ASTM-D6866 method.
 13. The method of claim 1 wherein said ester comprises a radiocarbon signature of at least 53.75 pMC when calculated according to the ASTM-D6866 method.
 14. The method of claim 1 wherein said ester comprises a radiocarbon signature of 107.5 pMC when calculated according to the ASTM-D6866 method.
 15. The method of claim 1 wherein said 1,3-propanediol portion of said ester has at least one of the following characteristics: 1) an ultraviolet absorption of less than about 0.200 at 220 nm and less than about 0.075 at 250 nm and less than about 0.075 at 275 nm; 2) a composition having L*a*b* “b*” color value of less than about 0.15 and an absorbance of less than about 0.075 at 270 nm; 3) a peroxide composition of less than about 10 ppm; and 4) a concentration of total organic impurities of less than about 400 ppm.
 16. A method of reducing the anthropogenic CO₂ emission of a detergent composition upon biodegradation, the method comprising: preparing a detergent composition comprising an ester wherein said ester is a biologically-derived, biodegradable 1,3-propanediol ester, and wherein said biologically-derived, biodegradable 1,3-propanediol ester exhibits no anthropogenic CO₂ emission upon biodegradation, and using said detergent composition whereby said detergent composition biodegrades, wherein said reduction of anthropologic CO₂ emission is compared to the anthropologic CO₂ emission of a detergent composition not comprising biologically-derived, biodegradable 1,3-propanediol ester.
 17. A method of producing an environmentally friendly detergent composition comprising: combining ingredients to make said detergent composition wherein said ingredients comprise an ester wherein said ester is a 1,3-propanediol ester, wherein the 1,3-propanediol portion of said ester is biologically-derived and biodegradable, and wherein said 1,3-propanediol portion of said ester exhibits no anthropogenic CO₂ emission upon biodegradation.
 18. The method of claim 17 wherein the detergent composition comprises between about 0.1% to about 80% biodegradable 1,3 propanediol ester.
 19. The method of claim 17 wherein said ingredients further comprise one or more components selected from the group consisting of: emulisifers, builders, conditioners, pearlizing agents, colorants, pigments, opacifiers, surfactants, gelling agents, structurants, thickeners, humectants, enzymes, polymers, bleaching agents, bleach surfactants, catalyst components, temperature stabilizers, chemical stabilizers, actives, hydrotropic agents, antioxidants, fragrances, sterilizers, and solvents.
 20. The method of claim 17 wherein the detergent is selected from the group consisting of liquid soaps, liquid detergents, household cleaning products, and industrial cleaning products. 